Composition for destruction of stable oil-water emulsions and protection of oilfield equipment from asphaltoresinparaffin deposits

 

(57) Abstract:

The invention relates to oil and the oil industry and can be used to destroy stable oil-water emulsions and protection of oilfield equipment from asphaltoresinparaffin sediments. The composition contains 20-80 wt.% polyoxyethylene condensation products of alkylphenol with the number of carbon atoms of the C4-C12in the alkyl chain and formaldehydefree component at a molar ratio of alkylphenol and formaldehydefree product 1:(0,67-1,0) in terms of formaldehyde, with a degree of oksietilirovannye 20-80 wt.% or a mixture of these products of condensation and blockcopolymer oxides of ethylene and propylene selected from the group comprising copolymers of ethylene oxides and propylene glycol-based or glycerine, the product of the interaction of blockcopolymer oxides of ethylene and propylene with phosphorus or phosphorus - and nitrogen-containing compounds; the product of the interaction of a mixture of blockcopolymer oxides of ethylene and propylene with the ethoxylated amine based fatty acid with phosphorus-containing compound (the rest up to 100 wt.%). In an advantageous embodiment, the composition further comprises a solvent. The invention photoprotective equipment and effectively solves the problem of wastewater treatment in the preparation of the oil. 1 C.p. f-crystals, 3 tables.

The invention relates to oil and the oil industry and can be used to destroy stable oil-water emulsions and protection of oilfield equipment from asphaltoresinparaffin deposits (ARPD).

Known composition for breaking oil-water emulsions, comprising the condensation product of an alkylphenol with 4-12 carbon atoms in the alkyl chain with high-boiling by-product of the production of isoprene from isobutylene and formaldehyde or 4,4-dimethyldioxanes-1,3, block copolymers of ethylene oxides and propylene-based glycol, a product of the interaction of simple polyester with the diisocyanate and the solvent (RF patent 2126030, MKI With 10 G 33/04, 1999).

The disadvantage of this composition is the selectivity with respect to oils with a specific composition.

Known demulsifier for breaking oil-water emulsions obtained by condensation of alkylphenol with 4-12 carbon atoms in the alkyl chain with high-boiling by-product of the production of isoprene from isobutylene and formaldehyde or 4,4-dimethyldioxanes with subsequent oksietilirovannye condensation product (RF patent 2037511, MKI With 10 G 33/04, 1995).

This Davidovich deposits.

The closest in technical essence of the present invention is a demulsifier for oil-water emulsions "Polina-D, including a mix of oxyalkylene Ethylenediamine (Deproxin-157) and oxyalkylene economicperformance resin at a mass ratio of 1: (0.25 to 5,6), respectively, in an organic solvent at a ratio of wt. %: the specified mix - 55-65; solvent - rest (RF patent 2139317, MKI C 10 G 33/04, 1999).

Known composition are not sufficiently effective against resistant water-oil emulsions formed of resin and paraffin oil, has a selective effect.

The present invention is the task of creating a highly effective composition for destruction of stable oil-water emulsions formed by oils containing asphaltenes, resins, paraffins, which simultaneously protects oilfield equipment from asphaltoresinparaffin sediments and can effectively solve the problem of wastewater treatment in the preparation of the oil.

The problem is solved so that the composition for the destruction of stable oil-water emulsions and protection of oilfield equipment from the asphalt is hydrated condensation product of alkylphenol and formaldehydefree component, as blockcopolymer oxides of ethylene and propylene contains block copolymers selected from the group comprising BSOAP based on glycol or glycerol, a product of the interaction of BSOAP with phosphorus or phosphorus - and nitrogen-containing compounds, the mixture BSOAP with the ethoxylated amine based fatty acid with phosphorus-containing compound, and oxyethylated condensation product of an alkylphenol with formaldehydefree component has in the alkyl chain, the number of carbon atoms of the C4-C12when the molar ratio of alkyl phenol : formaldehydefree component 1: (0,67-1,0) in terms of formaldehyde with a degree of oksietilirovannye 20 to 80 wt.%, or a mixture of these ethoxylated products of condensation, in the following ratio, wt.%:

The above ethoxylated condensation product or a mixture mentioned the condensation products of polyoxyethylene - 20 - 80

BSOAP selected from the above group - Rest

In an advantageous embodiment, the composition further comprises a solvent in the following ratio, wt.%:

Specified oxyethylated condensation product or a mixture of these hydroxy - leaded products of condensation-the spruce - Else

The condensation products of alkylphenol with the number of carbon atoms4- C12in the alkyl radical and formaldehydefree get component in a known manner the condensation of phenol and formaldehyde when heated in the presence of an acidic catalyst [A. Knop , SAB Century Phenolic resins and materials on their basis. - M.: Chemistry, 1983, S. 39]. To obtain the offered product condensation process is conducted at a molar ratio of alkyl phenol: formaldehydefree component equal to 1:(0,67-1,0) in terms of formaldehyde.

Oxyethylated condensation product of alkylphenol and formaldehydefree get component in a known manner oksietilirovannye when heated in the presence of an alkaline catalyst.

The degree of oksietilirovannye in the proposed product is 20 to 80 wt. %.

Example of getting a condensation product of alkylphenol and formaldehydefree product.

The reactor is placed 220 g (1 mol) of isononylphenol, 81 ml of 37% technical formalin (1 mol of formaldehyde) and 1.25 g, benzosulfimide. Then poured 400 g nefras Ar 120/200 and warm for 3-4 h at boiling temperature. After this time gradually raise the temperature of ablaut 10 ml of a saturated solution of lye.

Oxoethylidene carried out in a conventional autoclave method to the content of hydroxyethyl groups in the resulting product 50 wt.%.

As ALKYLPHENOLS (AF) with the number of carbon atoms WITH4-C12in the alkyl moiety can be used, for example, isooctylphenol on THE 6-14-579-E, or isononylphenol on THE 38-602-09-20-91, or tertbutylphenol on THE 2425-001-11003042-95, or undecadienal on 6-09-11-892-77,

As formaldehydefree component (FC) use water or water-methanol solution of formaldehyde (FMN) or paraform. An aqueous solution formaldehyde - formaldehyde is used in accordance with GOST 1625-89 "Formalin technical", paraform on THE 6-09-141-03-83, water-methanol solution of formaldehyde in accordance with THE 38-602-09-43-92.

As blockcopolymer oxides of ethylene and propylene can be used, for example, block copolymers of ethylene oxides and propylene glycol-based or glycerine, or amine.

As copolymers of ethylene oxides and propylene-based glycols can be used, for example, polyester simple 4202-2B-30 (4202) TU 2226-039-05766801-95, which is a simple polyester obtained ALCOHOLATES polymerization of ethylene oxides and propylene glycol, and the UB>SNSN2O)mR(OCH3SNSN2)m(OCH2CH2)nHE

< / BR>
2m = 59 - 64; 2n = 34 - 38 (RF patent 2078095, MKI With 10 G 33/04, 1997 ).

or the product of the interaction of copolymers of ethylene oxides and propylene glycol-based or glycerine with a phosphorus-nitrogen-containing compounds (BS-11) (RF patent 2069669, MKI 08 G 65/32, 1996), or the product of the interaction of a mixture of copolymers of ethylene oxides and propylene with the ethoxylated amine based fatty acid with phosphorus-containing compound (BS-III) (RF patent 2152422, MKI With 10 G 33/04, 2000), or the product of the interaction of copolymers of ethylene oxides and propylene glycol-based or glycerine, or amine with phosphorus-containing compound (BS-IV) (RF patent 2154090, MKI With 10 G 33/04, 2000).

As copolymers of ethylene oxides and propylene-based glycerol can be used, for example, polyethers obtained ALCOHOLATES polymerization of propylene oxide with glycerol, followed by blockcopolymers with ethylene oxide with a molecular weight of 3000 - 6000.E.: Laprol 3603-2-12 (L-3603) TU 2226-015-10488057-94, or Laprol 5003-2-15 (L-5003) TU 2226-006-10488057-94, or Laprol 6003-2B-18 (L-6003) TU 2226-020-10488057-94, or phosphorus-nitrogen oxides block copolymers of ethylene and p is to be used, for example, nefras-AR120/200the mixture of aromatic hydrocarbons in THE 38-101809-90, or butylbenzene fraction (BBF) TU 2411-034-05757601-94, or toluene according to GOST 5789-78, or ethylbenzene by THE 6-01-10-37-78, or xylene fraction on THE 2414-319-05742746-97, or a mixture of aromatic hydrocarbons and aliphatic alcohols, or mixtures thereof with2-C4-monoalkylamines esters of ethylene and diethylenglycol, or a mixture of aromatic hydrocarbons, aliphatic alcohols and water.

As the aliphatic alcohols can be used, for example, methyl alcohol (MS) according to GOST 2222-78, or ethyl alcohol (ES) according to GOST 18300-87, or isopropyl alcohol (IPA) according to GOST 9805-84.

As WITH2-C4-monoalkyl ethers of ethylene and diethylenglycol can be used, for example, monotropy ether of ethylene glycol (ethyl cellosolve), MEEEH on THE 6-09-3222-79, or BEEG - monobutyl ether of ethylene glycol (butylcellosolve) TU 6-01-646-84, or MADAG - monobutyl ether of diethylene glycol (butylcarbamoyl) TU 6-09-3289-79.

The analysis selected in the search process known solutions showed that in science and technology there is no object, analogous to the claimed combination of features, high demulsifying effect and protection shall be the sewage problem, on what basis can you conclude about the relevance of the proposed technical solutions to the criterion of "inventive step".

To prove compliance of the proposed solution the criterion of "industrial applicability" cited specific examples of the preparation of composition.

Example 1. To 50 g of the condensation products of 1 mol of isononylphenol and 0.9 mol of formaldehyde are added 50 g of blockcopolymer oxides of ethylene and propylene-based glycerol Lapola 6003-2B-18 (L-6003). The mixture was thoroughly stirred at 50 - 60oTo obtain a homogenous product.

Examples 2 to 31 perform similarly to example 1, changing the qualitative and the quantitative ratio of the components.

The composition of the proposed facility are presented in table. 1.

The resulting product is a viscous liquid from light yellow to dark brown color.

The compositions obtained according to examples 1 -31, dissolve in solvents.

Example 32. To 70 g of composition 1 add 30 nefras AP120/200. The mixture was thoroughly stirred to obtain a homogeneous product.

Examples 33 to 53 perform analogously to example 31, by changing the composition of components.

Example 54 - prot is m2/s, pour point -50oWith up to 60oC.

The proposed composition of the demulsifier in the solvent shown in table. 2.

The proposed demulsifier have demulsifying the effectiveness of natural and artificial water-oil emulsions.

Artificial emulsion 30% water cut is prepared in anhydrous coal Romashkinskoye oil field and model of the reservoir water. Anhydrous oil has a density 0,868 g/cm3. Mineralization model produced water used to prepare the emulsion, 200 g/l, a density of 1.12 g/cm3.

For testing use natural emulsion of oils 1 and 2 of the following composition:

Oil 1 contains, wt%:

Sulfur - 1,5

Resin acid - 32

Resin silikagelevye - 17,86

Asphaltenes - 2,32

Paraffin - 5,16

Density at 20oC - 0,867 g/cm3.

The viscosity at 20oC - 31,1 cSt (mm2/s).

Oil 2 contains, wt%:

Resin excise - 67

Resin silikagelevye - 22

Paraffin - 0,5

Density at 20oC - 0,946 g/cm3.

The viscosity at 20oC ) - 350 cSt (mm2/s).

The water content is 30% and straciatella Wagner for 30 min at room temperature. Then termostatic at 40oC for 2 h and measure the number of free spin-off of water.

The determination of the content of residual water in the oil is carried out in accordance with GOST 14870-77 method Dean-stark.

The degree of wastewater treatment is determined according to the method described in OST 39-133-81 "Water flooding of oil reservoirs. Determination of the oil content in produced water" and judged by the content of oil in waste water.

The test results demulsifying activity and the level of wastewater treatment is presented in table. 2 and 3.

The effectiveness of prevention asphaltoresinparaffin sediments evaluated on the following parameters:

- to launder film of oil;

- largest particle dispersion;

- to launder ARPD.

Determination of washing the oil film in the following order. In a glass tube to a certain label pour the oil treated with the reagent from the calculation of 0.005% on an active basis, and stand for 20 minutes and Then the oil was poured in a test tube halfway pour produced water, add oil up to the mark, the tube closes polished tube. Then on stopwatch tube periodoi instead of oil. The result is excellent, if when 70% of the area is over 30, good for 60 s and satisfactory for 180 C.

The dispersion of paraffin and washing the surface. These two methods are combined in one laboratory procedure and are carried out in a conical flask, which is placed in 50 ml of produced water, dispense the test reagent. In the same flask of paraffin weighing 0.5 g

The contents of the flask are heated to melt the wax (60 - 90oC) and then cooled stirring. After cooling to 20 to 25oTo measure the particle size of the dispersion of paraffin () and the surface area of the bulb, not covered (daubed) partynational (S).

According to the method, the result is considered excellent when the value of the variance of 0.1-1 mm, good when the value of variance of 2-5 mm, unsatisfactory when the value of variance of > 5 mm

In the evaluation method of washing the deposits from the surface, the result is considered excellent if the share of natural stone from ASPO surface S is 90-100%, good - 80-90%, satisfactory - 50-80% bad <50%.

Presented in the data tables it is seen that the composition effectively destroys persistent in the tion of paraffin and can effectively solve the problem of wastewater treatment in the preparation of the oil.

1. Composition for destruction of stable oil-water emulsions and protection of oilfield equipment from asphaltoresinparaffin deposits, including block copolymers of ethylene oxides and propylene and oxyethylated condensation product of alkylphenol and formaldehydefree component, characterized in that the ethoxylated condensation product of alkylphenol and formaldehydefree component has in the alkyl chain, the number of carbon atoms of the C4-C12when the molar ratio of alkylphenol and formaldehydefree component 1: (0,67-1,0) in terms of formaldehyde, with a degree of oksietilirovannye 20-80 wt. %, or a mixture of these ethoxylated products of condensation, and as blockcopolymer oxides of ethylene and propylene composition contains copolymers selected from the group comprising copolymers of ethylene oxides and propylene glycol-based or glycerine; the product of the interaction of copolymers of ethylene oxides and propylene with phosphorus or phosphorus - and nitrogen-containing compounds; the product of the interaction of a mixture of blockcopolymer oxides of ethylene and propylene with the ethoxylated amine based fatty acid with phosphorus-containing compound in the following ratio, wt is ondensation - 20 - 80

Block copolymers of ethylene oxides and propylene selected from the above group - Rest

2. Composition under item 1, characterized in that it further comprises a solvent in the following ratio, wt. %:

Specified oxyethylated condensation product or a mixture mentioned the condensation products of polyoxyethylene - 20 - 80

Block copolymers of ethylene oxides and propylene selected from the above group - 15 - 75

Solvent - Rest

 

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