Calcium removal from crude oil method

FIELD: oil-and-gas production.

SUBSTANCE: invention related to a method of calcium content decrease in fluid hydrocarbon medium, which includes contacting of mentioned above fluid hydrocarbon medium with a sequestrant, represented with a carboxylic acid for calcium containing separating complex formation, b. contacting of mentioned above fluid hydrocarbon medium with water medium for emulsion formation, in which after the mentioned above emulsion separation, at least part of the mentioned separated calcium containing complex stays in the water medium, and contacting the mentioned water medium with water soluble or water dispersing polymer, with I formula for the calcium disposals inhibition on surfaces, contacting with the mentioned above water medium, where the polymer has: (I) formula, where E - is a repeating fragment, which remains after non-saturated ethylene type compound polymerization, R1 is a hydrogen atom or the lowest (C1-C6)- alkyl or carbonyl, Q - is O or NH, R2 - is the lowest (C1-C6)-alkyl, hydroxy - substituted the lowest (C1-C6)-alkyl, the lowest (C1-C6)-alkyl sulfonic acid -(Et-O)-n, -(iPr-O)-n or -(Pr-O-)n, where n - is a variable from around 1 up to 100, and R3 - is a hydrogen atom or XZ, where X - is anion radical, selected form a group, consisting from SO3, PO3 or COO, Z - is hydrogen atom or atoms or any other water soluble cationic fragment, which serves is a balance in X anion radical valence; F - when presented, is a repeating fragment with a II: formula, where X and Z are the sane as in I formula, R4 - is a hydrogen atom or (C1-C6) the lowest alkyl, R5 - is hydroxy - substituted alkyl or alkylene, which has from 1 to 6 atoms, and XZ can or can not to be presented, c and d - are positive whole numbers, e is not-negative number, and j is equal to 0 or 1.

EFFECT: calcium disposal decrease on a surfaces contacting with water phase water in oil separated emulsion.

21 cl, 7 ex, 7 tbl

 

The technical FIELD TO WHICH the INVENTION RELATES.

The invention relates to improved methods of removal of calcium from hydrocarbon medium by extraction under the action of sequestrant. Prescribe, when added to a hydrocarbon medium, leads to the formation of calcium complex, which passes into the aqueous phase, when the hydrocarbon medium is brought into contact with the phase of the wash water. Specifically receptorligand controlling the deposition agent is brought into contact with an aqueous phase to control the education is based on the calcium deposits.

The LEVEL of TECHNOLOGY

All crude oil contains impurities that cause corrosion, clogging of the heat exchanger, the coking in the furnace, deactivation of the catalyst, and the deterioration of the quality of the product at the processing plant, and other processes. These pollutants are widely classified as salt, bottom sediment and water (BS+W), particulate matter and metals. The amount of these impurities varies depending on the characteristics of crude oil. In General, the salt content of the crude oil in the range of about 3-200 pounds per 1000 barrels (ptb).

Saturated salt solutions present in raw, include mainly sodium chloride with lesser amounts of magnesium chloride and calcium chloride, which are also present. Chlorides are the main the source of highly corrosive HCl, which severely damages the gutter towers processing plant and other equipment. In addition, carbonates and sulfates may be present in raw in sufficient quantities to contribute to scale formation in the preliminary heat exchanger crude oil.

Solids other than salt are equally harmful. For example, sand, clay, volcanic ash, drilling mud, rust, iron sulfide, metal and slag may be present and cause clogging, clogging, abrasion, erosion and contamination of the final product. As a source of waste and pollution, deposition stabilizes the emulsion in the form moistened with oil of solid products, and can carry a significant amount of oil in waste management systems.

Metals in raw can be an inorganic or ORGANOMETALLIC compounds, which consist of combinations of hydrocarbons, arsenic, vanadium, Nickel, copper and iron. These materials contribute to clogging and can cause poisoning of the catalyst in the subsequent processes of the processing plant, such as catalytic cracking processes, and they can also contaminate the final products. Most metals are in the bottom remains in the processes of the processing plant. When the bottom remainders are powered, for example, for the stop for coking, the contamination of the final coke is particularly undesirable. For example, in the manufacture of electrodes of the high quality of the coke, iron impurities from a coke can lead to reduced efficiency of the electrode and a breakdown in processes such as those used in the industrial production of chlorine and alkali.

Desalting is, as the name implies, a process specially adapted for the initial removal of inorganic salts from crude before cleaning. Stage desalting is achieved by adding and mixing with raw small percentage of the volume of clean water for contact with saturated salt solution and salt. When the desalting of crude oil emulsion water in oil (W/O) purposefully formed with water, added in amounts of about 4 to 10 vol.%, counting on crude oil. Water was added to the crude and mixed thoroughly to transfer impurities from raw water phase. Phase separation is due to the merging of small splashes of water and a gradual increase in inclusions and possible gravity separation of oil and below the water phase.

Demulsification agents are usually added in the upper stream of the plant for desalination to help ensure maximum mixing oil and water phases in the plant for desalination, and moderate is velichenie speed water separation. Known demulsifying agent includes water-soluble salts, from sulphonated glycerides, from sulphonated oils, resins based on alkoxysilane the phenol-formaldehyde, a polyalcohol, copolymers of ethylene oxide and propylene oxide, a variety of polyester materials and many other commercially available compounds.

Plants for desalination are also usually equipped with electrodes to create an electric field in the plant for desalination. It serves to polarize the dispersed water molecules. Thus formed by the dipole of the molecule result in the force of attraction between oppositely charged poles, with increasing gravity velocity merge droplets of water rise from 10 to 100 times. Blotches of water is also moving quickly in an electric field, thus causing accidental collision, which further enhances the merger.

After separation of the phases of the emulsion water in oil, the raw material is usually removed from the top of plants for desalination and sent to distillation column in sections crude oil or other processes at the processing plant. The aqueous phase can be skipped through the heat exchangers or similar devices and eventually excreted in the form of sewage.

Remove calcium is an important task for th the wifi several years due to the increasing use of crude oil with very high levels of calcium (such as some of the oil from the African continent, which contain more than 200 ppm, and some close to 400 ppm calcium). Previously the maximum calcium content was 50 ppm Extraction of calcium salts by the method of desalting difficult if the calcium is associated with naphthenic acids (crude oil with high TAN (total acid number)). These naphthenate calcium not extracted with water and remain in the oil phase. Problems refiners associated with a high content of calcium include metal content, increased for fuel oils, which are contained in the impurity distillation residues, poisoning of catalysts by end manufacturers catalytic cracking affects the specifications of coke on the metal, and contributes to the clogging of the segment of the crude oil and the gradual clogging of the coke oven.

Were first described several ways to remove calcium from crude oil, essentially using plants for desalination. All include the use of organic carboxylic acids (presumably for protonation of naphthenic acids, and extraction of calcium in the wash water). Reynolds (Reynolds (Reynolds)) (U.S. patent 4778589) describes the use hydroxycarbonic acids, such as citric acid, is added to the wash water for sodas is via extraction of calcium in the plant for desalination. Rowling (Roling) (U.S. patent 5078858) improved this method by adding citric acid to the phase of crude oil to increase the speed of extraction of metals. Both patents discuss the modification of the pH of wash water for best extraction. Lindemuth (Lindemuth) (U.S. patent 5660717) describes the use of functionalized polymers of acrylic acid to remove cations. Nguyen (Nguyen) (published patent application U.S. 2004/0045875) describes the use of alpha-hydroxycarbonic acid (especially glycolic acid) to remove calcium and amines.

The way Reynolds (Reynolds), which is likely to be successful in the extraction of calcium from low levels (<30 ppm), has two significant drawbacks that make it not applicable to crude oils with a high content of calcium. One is that, as the method of extraction is stoichiometric, with high levels of citric acid required in the wash water, its pH drops significantly (below 3) and causes corrosion damage in the path of flushing water. It can be mitigated by the use of corrosion inhibitors.

The second drawback is that the final concentration of calcium citrate has a limit of solubility, approximately 1000 ppm at room temperature, and pH 6-8 solubility inversely correlated with temperature. the thus, the you can see that the deposited layer of calcium citrate is a problem with typical temperatures in the plant for desalination (250°F-300°F) and concentrations occurring when extracted higher levels of calcium, typically with a 5% rate of wash water. In fact, both of these faults occur during operation of the processing plant when processing citric acid significant volumes of crude oil with a high content of calcium. One problem that is investigated, represents deposition in a heat exchanger and transport pipeline from the saturated salt solution.

The INVENTION

The invention relates to the combination of methods of chemical treatment to overcome the shortcomings of the patent Reynolds (Reynolds). In one aspect the invention relates to the use of sequestrant for effective removal of calcium from hydrocarbon medium in the aqueous phase of the emulsion water in oil, United in contact with the aqueous phase by specially receptorligand controlling the deposition of the polymer, for inhibition, thus, education is based on calcium scale and Deposit in the aqueous phase and on the surfaces of the system processing plant, which are in contact with the aqueous phase. Examples of such surfaces include drainage pipes, sewage line is botflies, the capacity of plants for desalination, mixing valves, stationary mixers, and heat exchangers that are in contact with saturated salt solution (i.e. water phase).

In a more preferred aspect of the invention citric acid or its salts are used as sequestrant, and detachable containing calcium complex is a calcium citrate. Controlling the deposition of the polymer inhibits scale formation of calcium citrate in the aqueous phase and on surfaces that come into contact with the aqueous phase. While controlling the deposition of calcium citrate is important that the treatment should not adversely affect the operation of the plant for desalination (longer deposition rate of the water, and so on).

A DETAILED DESCRIPTION of the PREFERRED embodiments

Although the present invention is initially described in connection with its use in the traditional operation of the plant for desalination, the person skilled in the art will appreciate that other methods of extraction will also benefit from the invention. One example is a counter-current extraction, in which the aqueous phase is brought into contact with current in the opposite direction hydrocarbon environment.

Further, although the invention is particularly pleased with the output when removing calcium from crude oil, the phrase "liquid hydrocarbon medium" should be understood as including other environments, such as bitumen, atmospheric or vacuum residues or neasfaltirovanyj solvent oil, produced from the residue of the crude oil, which are hydrobromide or krekingovogo to produce commercial products such as gasoil, gasoline, diesel fuel, bituminous shale, gasified coal, enriched tar Sands, etc. Also, the emulsion containing such a hydrocarbon environment or any petroleum product, are included within the scope of this phrase.

Crude oil with a high content of calcium, referenced herein, represent the crude oil with calcium content of more than about 30 ppm, there is a relatively one million parts of crude oil or other liquid hydrocarbon media. The invention will be particularly beneficial for those crude oils, which have a content of more than about 100 ppm of calcium, and higher.

Also, the phrase "detachable containing calcium complex", which is used in the detailed description and in the claims, covers a large range of chelated, komplikovanih, or separable complexes or ligands, or other drugs, including ionic or covalent compounds, in the form of calcium extragere is conducted from the oil phase and at least partially separated in the aqueous phase in the plant for desalination or other method of extraction. For example, when citric acid or one of its salt forms, used as a binder compounds, calcium citrate is formed as a detachable containing calcium complex, which at least partially separated in the aqueous phase during the separation of the emulsion water in oil.

As for sequestrants, which are added or to the oil phase or the aqueous phase in contact with raw high content of calcium, they are brought in at least stoichiometric quantities relative to the moles of calcium in the crude oil. Typical airing include airing the type of carboxylic acid, where the preferred airing include those that contain multiple COOH functions, such as dienone carboxylic acids, including oxalic, malonic, succinic, maleic and adipic acid. Most preferred are hydroxycarbonate acid, such as citric and tartaric acids and their salts.

In one typical embodiment of the invention, the liquid hydrocarbon environment carefully and thoroughly mixed with an aqueous solution of citric acid or its salts. Calcium in the liquid hydrocarbon is combined with sequestrants for the formation of water-soluble is or dispersible complex in the aqueous phase. Controlling the deposition of the polymer I, as described in further brought into contact with a complex way, such as adding it to the aqueous phase. The aqueous phase and the hydrocarbon phase separated in the separation of the emulsion water in oil, then separated hydrocarbon phase is subjected to distillation or hydrobromide.

As for the copolymer and ternary copolymers, which are used for inhibition of education based on calcium scale deposits, they are represented by the following formula I:

(I)

where E represents a repeating fragment remaining after polymerization of unsaturated compounds ethylene type; preferably carboxylic acid, sulfonic acid, phosphonic acid, or amide; R1represents a hydrogen atom or lower (C1-C6)-alkyl; G represents a lower (C1-C6)-alkyl or carbonyl; Q represents O or NH; R2is a low (C1-C6)-alkyl; hydroxy-substituted lower (C1-C6)-alkyl, lower (C1-C6)-alkylsulfonyl acid -(Et-O)-n, -(iPr-O)-nor -(Pr-O)-nwhere n is in the range from about 1 to 100, preferably 1 to 20, and R3represents a hydrogen atom, or XZ, where X is an anionic radical selected is from the group consisting of SO3, PO3or COO; Z represents a hydrogen atom or hydrogen atoms, or any other water-soluble cationic fragment, which serves as a counterbalance to the valence of the anionic radical X, including, without limitation, Na, K, Ca, NH4; j is 0 or 1.

F, when present, is a recurring fragment having the formula II:

(II)

where X and Z are the same as in formula I. R4represents a hydrogen atom or lower (C1-C6)-alkyl, R5represents a hydroxy-substituted alkyl or alkalinity radical having from 1 to 6 atoms, and XZ may be present or may not be present.

The indices c, d, and e in formula I represent the molar ratio of Monomeric repeating fragments. The ratio is not critical to the present invention, provided that the copolymer or ternary copolymer is water soluble or water dispersible. The indices c and d are positive integers, while the index e is a nonnegative integer. That is, c and d represent integers of 1 or greater, while e can be 0, 1, 2, etc.

As for group E in the formula I, the group may include a repeating fragment obtained after polymerization of carboxylic key is lots sulfonic acid, phosphonic acid, or amide form, or a mixture thereof. Typical compounds include, without limitation, recurring fragment remaining after polymerization of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, maleic acid or its anhydride, fumaric acid, basis of itaconic acid, styrelseledamot acid, vinylsulfonic acid, isopropylphenol acid, vinylphosphonic acid, vinylidenechloride acid, 2-acrylamide-2-methylpropanesulfonic acid; and the like, and mixtures thereof. Water-soluble salt forms of these acids are also within the scope of the present invention. More than one type of Monomeric fragment E may be present in the polymer of the present invention.

Typical copolymers and ternary copolymers, include formula, include:

1) copolymer of acrylic acid/allyl-2-hydroxypropanesulfonic ether (i.e. AA/AHPSE);

2) copolymer of acrylic acid/allyltriethoxysilane ether (i.e. AA/APES);

3) copolymer of acrylic acid/2-acrylamide-2-methyl-1-propanesulfonic acid (i.e. AA/ AMPS);

4) ternary copolymer of acrylic acid/ammonium allyltriethoxysilane/ alloxy-2-hydroxypropane-3-sulfonic acid (i.e. AA/APE/AHPSE);

5) ternary copolymers of acrylic acid/methacrylic acid/ammonium, allpolitics(10)sulfate (i.e. AA/MA/APES);

6) ternary copolymers of acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/ammonium allyltriethoxysilane (i.e. AA/AMPS/APES).

Polymerization of the copolymer and/or a ternary copolymer (I) can be carried out according to the methods of solution polymerisation, emulsion, micelle or dispersion. Can be applied by conventional polymerization initiators such as persulfates, peroxides, and azoinitiator. The polymerization can also be initiated by the mechanism of radiation or ultraviolet radiation. Can be applied reagents transfer circuit, including alcohols, such as isopropanol or allyl alcohol, amines, mercaptoethane or hypophosphite acid to regulate the molecular weight of the polymer. One particularly preferred method is to use hypophosphoric acid as reagent transfer circuit in such a quantity that a small part of them remains in the polymer chain (i.e., from about 0.01-5 wt.%). Can be added razvitsya agents, such as methylenebisacrylamide, or diacrylate of polyethylene glycol, and other multifunctional crosslinking agents. The resulting polymer may be isolated by precipitation or other well known techniques. If polymerizate is carried out in aqueous solution, the polymer can be applied simply in the form of an aqueous solution.

Molecular weight water-soluble copolymer of formula I is not critical, but preferably falls within a molecular weight from about 1,000 to 1,000,000; more preferably, from about 1,000 to 50,000 and most preferably from about 1500 to 25000. The essential criterion is that the polymer was water soluble or water dispersible. The metal-binding compound may be brought into contact with a liquid hydrocarbon medium or by adding sequestrant to the liquid hydrocarbon medium, or to the wash water in the plant for desalination. As mentioned above, the contact of the hydrocarbon environment to prescribe forms a detachable containing calcium complex, which at least partially separated in the aqueous phase when the water separates from the oil emulsion in the plant for desalination or other method of extraction.

The polymer I can be brought into direct contact with the separated aqueous phase or can be thoroughly dispersed in the hydrocarbon environment for effective contact with the aqueous phase by mixing a liquid hydrocarbon medium and the water environment in the plant for desalination. Valid about 1-300 ppm polymer, based on one million parts of the aqueous phase. More preferably, about 1-100 ppm polymer I primestats is to the aquatic environment.

In conventional apparatus for desalting, the emulsion may be heated to about 100°F-300°F, and the electric potential can be applied through the emulsion to enhance the separation. The use of polymer I helps to inhibit based on calcium deposition or scum, which must otherwise be formed in the aqueous phase or on surfaces that are in contact with them, such as piping, waste piping, heat exchangers saturated salt solution, the capacity of the plant for desalination, mixing valves, stationary mixers, and the like.

It can be noted that the removal of salts and solids from crude oil is traditionally held at the location of the processing plant, which has installed the appropriate equipment for washing of crude oil by water (that is, the installation for the desalination). Place oil in General have only separating equipment for the Department of concomitant or received water and leave the final removal of salts to the refiners. According to the invention the removal of salts can also be successfully carried out at the place of production. It may include the installation of equipment such as plants for desalination, but should lead to a consistent improvement of the obtained oil, and producing a product of higher quality.

Traditional de is alligatory can be added to the crude oil to enhance the separation of the emulsion. These demulsifiers are, for the most part, surface-active substances, which move on the surface of the separation of oil/water and change the surface tension of the interfacial layer, which allows the splashes of water or oil to blend in more easily. These demulsifiers reduce the time required for good separation of oil and water. In addition, in addition, the scale inhibitor should not significantly affect the characteristics of the demulsifier. In addition, traditional inhibiting corrosion agents may be added or the water or the oil phase, or both for inhibition of corrosion in the plant for desalination and corrosion, which may otherwise take place in the stream emanating from processes of hydrobromide and/or water treatment.

It is not clear that the polymers (I) are effective in inhibiting the deposition of calcium citrate. For example, as will be shown in the following examples, several well-known agents, inhibiting scale deposits of calcium carbonate, such as polyacrylic acid, HEDP (1-hydroxyethyl-1,1-diphosphonic acid) and NTA (nitrilotriacetic acid), have a small effect or no effect on the inhibition of the formation of calcium citrate.

Thus, for the first time it was shown that the family of polymers, namely, the polymer (I)inhibit the deposition of calcium citrate and make is possible to significantly higher levels, occur at elevated temperatures prior to the deposition. The invention is an additional technology that allows citric acid or other airing applied to the extraction of high concentrations of calcium from crude oil.

Hereinafter the invention will be described with reference to the following specific examples, which should be regarded solely as illustrative, and not limiting the scope of invention.

EXAMPLES

Example 1

In order to investigate the effectiveness of different selected substances for inhibiting the formation of crystals of calcium citrate, prepared solution (solution A) 1000 ppm (as solids) of calcium chloride, and 1000 ppm (as solids) of citric acid. Was added NaOH to bring the pH to a 7.1. This raw and processed later, the solution was heated at 100°C for 1-1 .5 hours. The results are presented in table 1.

Table 1
ProcessingObservations
1100 ml of solution A: rawA large number of small crystals precipitated on the bottom (presumably 100). Water is transparent.
2100 ml of solution A + diluted sulfuric acid to a pH of 5.1About 25% (compared to untreated) slowly crystallizes. Water is transparent.
3100 ml of solution A + diluted sulfuric acid to a pH of 6.1About 40% (compared to untreated) slowly crystallizes. Water is transparent.
4100 ml of solution A + 50 ppm active HEDP (DeQuest 2010)A large number of small and flocculent precipitate. The water is muddy.
5100 ml of solution A + 50 ppm active NTAA little (<2 - 5%) of crystals on the bottom. Water is transparent.
6100 ml of solution A + 50 ppm comparative product AAA large number of small and flocculent precipitate. The water is muddy.
HEDP = hydroxyethylidenediphosphonic acid.
NTA = nitrilotriacetic acid.
Comparative product AA = a homopolymer of polyacrylic acid, molecular weight of about 5,000.

<> Example 2.

Additional testing was done using the method of example 1. The results are shown in table 2.

Table 2
ProcessingObservations
2.1100 ml of solution A: rawA large number of small crystals precipitated on the bottom (presumably 100%). Water is transparent.
2.2100 ml of solution A + 10 ppm active NTAA large number of small crystals precipitated on the bottom (about 100%). Water is transparent.
2.3100 ml of solution A + 20 ppm active NTAA large number of small crystals precipitated on the bottom (about 60%). Water is transparent.
2.4100 ml of solution A + 30 ppm active NTAFewer small crystals precipitated on the bottom (about 30%). Water is transparent.
2.5100 ml of solution A + 40 ppm active NTA About 5% of the crystals at the bottom. Water is transparent.
2.6100 ml of solution A + 50 ppm active NTAVery small crystals at the bottom. Water is transparent.

Example 3.

Were carried out the following tests using the method of example 1. The results are presented in table 3.

Table 3
ProcessingWatched
3.1100 ml of solution A: rawA large number of small crystals precipitated on the bottom (presumably 100%). Water is transparent. 0,0595 g of crystals
3.2100 ml of solution A + 35 ppm active NTAAbout 5-10% of the crystals at the bottom. Water is transparent.
3.3100 ml of solution A + 35 ppm active, free from EDTA, acidAbout 5-10% of the crystals at the bottom. Water is transparent.
3.4100 ml of solution A + 70 ppm product A Clean and clear water. Crystals not.
3.5100 ml of solution A + 70 ppm of product BClean and clear water. Crystals not.
3.6100 ml of solution A + 70 ppm product PBTCAbout 5-10% of the crystals at the bottom. Water is transparent.
3.7100 ml of solution A + 70 ppm product DeQuest 2060Crystals is not observed, but the water is muddy.
3.10100 ml of solution A + 30 ppm of product AClean and clear water. Crystals not.
3.11100 ml of solution A + 50 ppm product AClean and clear water. Crystals not.
3.12100 ml of solution A + 70 ppm product AClean and clear water. Crystals not.
3.13100 ml of solution A + 30 ppm of product BClean and clear water. Crystals not.
3.14100 ml of solution A + 50 ppm product B Clean and clear water. Crystals not.
3.15100 ml of solution A + 70 ppm of product BClean and clear water. Crystals not.
3.16100 ml of the raw solution AA large number of small crystals precipitated on the bottom (presumably 100%), the water is transparent. 0,0644 g of crystals.
PBTC = 2-phosphonobutane-1,2,4-tricarboxylic acid.
DeQuest 2060 = dietilen-diaminopentane(methylenephosphonate acid).
Product a = copolymer of acrylic acid/allyl-2-hydroxypropanesulfonic ether (AHPSE); 36,5% active; nominal molecular weight of about 25,000; AA:AAPSE = 3 : 1;
Product B = a copolymer of acrylic acid/allyl, politicsi(10)ether sulfate (APES); % activity about 30%; nominal molecular weight of about 15,000. AA:APES = 3:1.

Example 4.

Additional tests were made using the methods of example 1. The test results presented in table 4.

Table 4
ProcessingObservations
1* 100 ml of solution A: rawA large number of small crystals precipitated on the bottom (presumably 100%), the water is transparent. 0,0692 g of crystals.
2100 ml of solution A +
5 ppm product A
About 5% of the crystals on the bottom of the water is transparent.
3100 ml of solution A +
10 ppm product A
Crystals no. Clear water.
4100 ml of solution A +
20 ppm product A
Crystals no. Clear water.
5100 ml of solution A + 5 ppm of product BAbout 5 - 10% of the crystals at the bottom. Water is transparent.
6100 ml of solution A + 10 ppm product BAbout 2 - 5% of the crystals at the bottom. Water is transparent.
7100 ml of solution A + 20 ppm of product BCrystals no. The water is clear.
8100 ml of solution A + 20 ppm active free from EDTA acidAbout 10-20% of Cristallo is at the bottom. The water is clear.
9100 ml of solution A + 20 ppm active NTAAbout 10-20% of the crystals at the bottom. The water is clear.
1* the solution was filtered through a Teflon filter and passed in neftehimichesky laboratory for analysis of calcium citrate. The analysis confirmed that the calcium citrate.

Example 5.

In order to investigate the influence of the reaction inhibiting deposits on the functioning of the installation for desalting were carried out model experiments on test samples of crude oil with a high content of Ca2+in the modeling apparatus for desalting.

Modeling plant for desalination includes a reservoir with an oil bath, equipped with multiple test tubes placed in her. The oil bath temperature can vary up to approximately 300°F to simulate real operating conditions. The electrodes during operation associated with each test tube for the message of the electric field of alternating potential through the test emulsion contained in test tubes.

95 ml of crude oil with a high content of calcium (110 ppm Ca2+) and 5 ml of deionized water were placed in each test tube in accordance with the test is the subject materials for processing. The processed mixture of crude oil-water homogenized by mixing with 13 psi (13000 rpm / 2 sec) and processed mixture of crude oil-water was heated to about 250°F. After 32 minutes, 75 ml of the upper part of the raw collected from each tube for the analysis of calcium. The falling water (i.e. water level) in ml was observed for each sample through a pre-defined intervals. The results are presented in table 5.

Table 5
The water level defined in ml
1 min2 min4 min8 min16 min32 minThe average water levelThe surface of section (I/F) & Saturated salineThe calcium content in the oil layer
5.18 ppm 2W158 to oil,40 μl (2%)3,545554,50Good10,9 ppm
1000 ppm of citric acid to the water50 ál (10%)I/F, clean water
5.28 ppm 2W158 to oil,40 μl (2%)3,744,55554,531 mlto 11.7 ppm
1600 ppm of citric acid to the water80 ál (10%) emulsion pure water
5.38 ppm 2W158 to oil,40 μl (2%)0,411,62,53,542,172 mlto 12.3 ppm
1000 ppm of citric acid to water,50 ál (10%)emulsion pure water
300 ppm of the product And to75 μl (2%)
water
5.48 ppm 2W158 to oil,40 μl (2%)0,40,81,422,531,682 mlof 11.0 ppm
1600 ppm of citric acid to water,80 ál (10%) emulsion pure water
300 ppm of the product And to the water75 μl (2%)
5.58 ppm 2W158 to oil,40 μl (2%)0,40,61,22,533,51,872 mlto 12.2 ppm
1000 ppm of citric acid to water,50 ál (10%)emulsion pure water
400 ppm of the product In water100 μl (2%)
5.68 ppm 2W158 to oil,40 μl (2%)0,20,411,61,82,51,252 mlto 13.6 ppm
1600 ppm lemon80 ál (10%)emulsion
acid to water,clean water
400 ppm of product100 μl (2%)
water
5.78 ppm 2W158 to oil,40 μl (2%)3 3,54,55554,33Goodof 13.3 ppm
1000 ppm lemon50 ál (10%)I/F, net
acid to water,water
800 ppm NTA to the water200 μl (2%)
5.88 ppm 2W158 to oil,40 μl (2%)3,544,55554,50Goodto 9.9 ppm
1000 ppm lemon50 ál (10%)I/F, net
acid to water, water
800 ppm EDTA to water200 μl (2%)
5.910 ppm 2W15850 μl (2%)0,40,61,22,73,53,72,022 mlNot defined
oil, 1000 ppm50 ál (10%)emulsion
citric acid totransparent
water,75 μl (2%)water
300 ppm of the product And to
water
5.1020 ppm 2W158100 μl (2%)0,81,22,53,74,552,95Goodof 10.4 ppm
oil, 1000 ppm50 ál (10%)I/F
citric acid totransparent
water,75 μl (2%)water
300 ppm of the product And to
water
5.1130 ppm 2W158 123,54,5553,50Goodof 10.4 ppm
oil, 1000 ppm50 ál (10%)I/F
citric acid totransparent
water,75 μl (2%) water
300 ppm of the product And to
water
5.1240 ppm 2W158200 μl (2%)2,53,5the 4.75554,2 Goodof 12.4 ppm
oil, 1000 ppm50 ál (10%)I/F
citric acid totransparent
water,75 μl (2%)water
300 ppm of the product And to
water
5.138 ppm 2W158 to oil,40 μl (2%)44,555554,75GoodNot defined
1000 ppm lemon50 ál (10%) I/F
acid to watertransparent
water
5.148 ppm 2W158 to oil,40 μl (2%)44,55555 4,75GoodNot defined
1000 ppm lemon50 ál (10%)I/F, the water
acid to water,slightly
150 ppm WS55 to the waterof 37.5 μl (2%)muddy
5.158 is a 2W158 oil40 μl (2%)44,555554,75GoodNot defined
1000 ppm lemon50 ál (10%)I/F, the water
acid to water,slightly
300 ppm WS55 to the water75 μl (2%)the muddy
5.168 ppm 2W158 to oil,40 μl (2%)44,555554,75GoodNot defined
1000 ppm lemon50 ál (10%)I/F
acid to water, transparent
15 ppm of the product And toof 3.75 μl (2%)water
water
5.178 ppm 2W158 to oil,40 μl (2%)44,555554,75GoodNot defined
1000 ppm lemon50 ál (10%)I/F, the water
acid to water,slightly
15 ppm of the product And toof 3.75 μl (2%)muddy
water,
150 ppm WS55 to the water37,5 (2%)
5.188 ppm 2W158 to oil,40 μl (2%)44,555554,75GoodNot defined
1000 ppm lemon50 ál (10%) I/F, slightly
acid to water,muddy water
15 ppm of the product And toof 3.75 μl (2%)
water,
300 ppm WS55 to the water75 (2%)
5.1925 ppm 2W158 to oil,125 μl (2%)44,555554,75GoodNot defined
1000 ppm of citric acid to water,50 ál (10%)I/F, slightly muddy water
15 ppm product And water,of 3.75 μl (2%)the
300 ppm WS55 to the water75 (2%)
2W158 = Demulsifier; available from GE Betz.
WS55 = corrosion inhibitor; available from GE Betz.
In experiments 5,1-5,12 products And & adversely affect the water levels at these very high (unrealistic) concentrations.
At these high concentrations, the required elevated levels of about 20-30 ppm 2W158 for complete digestion of the emulsion.
NTA and EDTA do not have a negative effect on the water level. With 40 ppm of the active substance, processing the aqueous phase to control the crystallization of the precipitate, it is necessary only 8 ppm 2W158 for detachment of all of the added water.
Conclusion: in a typical dosages processing (that is 15 ppm in water) of the product And there is no harm is its effect on the operation of the plant for desalination.

Example 6.

Was conducted additional tests using the technique of example 1. The results are shown in table 6.

Table 6
ProcessingObservations
Room temperature100°C After 1-1,5 hours
6.1100 ml of solution A: rawClear water, no precipitateA large number of small crystals precipitated on the bottom (presumably 100%), the water is transparent.
6.2100 ml of A 10 ppm product A (50 ál of a 2% solution in water)Clear water, no precipitateVery few small crystals on the bottom (<1% compared with the standard). Clear water.
6.3100 ml of solution A +10 ppm of product A (50 ál of a 2% solution in water), 200 ppm WS-55 (200 μl of 10% solution in water)Muddy water, no precipitateAbout 10% of the crystals of the adhesive is about on the walls and on the bottom (compared with standard). Muddy water
6.4100 ml of solution A +20 ppm of product A (100 µl, 2% solution in water) 200 ppm WS-55 (200 µl, 10% in water)Muddy water, no precipitateVery few small crystals on the bottom (<1% compared with the standard - just as in #2). Muddy water.
Conclusion:
1. 200 ppm WS-55 causes the turbidity of the water. This also affects the characteristics of the product A.
2. 20 ppm of A product (instead of 10 ppm) lead to the disappearance of crystals in 100 ml of solution A, in the presence of processing 200 ppm WS-55.

Example 7.

Conducted the following series of tests using the techniques described in example 1. The results are presented in table 7.

Table 7
ProcessingObservations
Room temperature100°C after 1-1,5 hours
7.1100 ml of solution A: rawClear water, no precipitate.A large number of small crystals fell in OSA is OK on the bottom; water is transparent.
7.2100 ml of solution A + 2,5 ppm active product AClear water, no precipitate.Sludge is not observed, clear water.
7.3100 ml of solution A + 5 ppm of active product A.Clear water, no precipitate.Sludge is not observed, clear water.
7.4100 ml of solution A +10 ppm of active product A.Clear water, no precipitate.Sludge is not observed, clear water.
7.5100 ml of solution A + 2,5 ppm active product CClear water, no precipitate.Sludge is not observed, clear water.
7.6100 ml of solution A + 5 ppm of active product CClear water, no precipitate.Sludge is not observed, clear water.
7.7100 ml of solution A + 10 ppm of active product CClear water, no precipitate. Sludge is not observed, clear water.
Product C is a copolymer of acrylic acid/2-acrylamide-2-methylpropane-3-sulfonic acid with a molecular weight of about 4500.

You may notice that when used in the description and the subsequent claims, determining that the liquid hydrocarbon medium or aqueous medium are in contact with the agent, it should not exclusively be interpreted to mean that the agent is added directly to the mentioned environment in contact. Instead, the agent can be added to another environment or to the emulsion containing the expected environment, provided that at some point in the process, the agent, where it was added in the process, can, ultimately, to mix with or to communicate with the intended environment.

While we have presented and described herein certain embodiments of the present invention, it is understood that with the same success can be covered with any change or modification; which can be made without deviating from the spirit and scope of the invention as defined in the attached claims.

1. A method of reducing the calcium content in the liquid hydrocarbon medium, which includes
a) contacting mentioned liquid hydrocarbon environment sequestrants, pre the excitation carboxylic acid for the formation of a detachable containing calcium complex;
(b) contacting mentioned liquid hydrocarbon medium with an aqueous medium to form an emulsion, in which after the separation of said emulsion at least part of these separated calcium complex remains in the above-mentioned aqueous medium; and (C) contacting the aforementioned aqueous medium with a water-soluble or water-dispersible polymer having the formula I for inhibiting the formation of calcium deposits on surfaces in contact with said aqueous medium, where the said polymer has the formula

where E represents a repeating fragment remaining after polymerization of unsaturated compounds ethylene type; R1represents a hydrogen atom or lower (1-C6)-alkyl; G represents a lower (C1-C6)-alkyl or carbonyl; Q represents O or NH; R2represents the lowest (1-C6)-alkyl; replacement lower (1-C6)-alkyl, lower (C1-C6)-alkylsulfonyl acid -(Et-O)-n, -(iPr-O)-nor -(Pr-O)nwhere n varies from about 1 to 100, and R3represents a hydrogen atom or XZ, where X is an anionic radical selected from the group consisting of SO3, RHO3or COO; Z represents a hydrogen atom or at the we of hydrogen or any other water-soluble cationic fragment, which serves to counterbalance the valence of the anionic radical X; F, when present, is a recurring fragment having the formula II

where X and Z are the same as in formula I; R4represents a hydrogen atom or (C1-C6)-lower alkyl, R5is a replacement alkyl or alkylene having from 1 to 6 atoms, and XZ may be present or not be present; C and d are positive integers, f is a nonnegative integer, and j is 0 or 1.

2. The method according to claim 1 in which from about 1 to 300 ppm from the above-mentioned polymer (I) is brought into contact with the said aqueous medium, counting on one million parts referred to the aquatic environment.

3. The method according to claim 2, where from about 1 to 100 ppm of the above-mentioned polymer (I) is brought into contact with the said aqueous medium.

4. The method according to claim 3 where the above-mentioned liquid hydrocarbon medium has a calcium content greater than about 30 ppm of calcium, counting on one million parts mentioned liquid hydrocarbon medium.

5. The method according to claim 4 where the above-mentioned liquid hydrocarbon medium is a crude oil.

6. The method according to claim 5, where referred to prescribe is a citric acid or its salt, and where the aforementioned detachable containing calcium complex is a t the expenses of calcium.

7. The method according to claim 6, where the said polymer I is a representative or representatives selected(mi) from the group consisting of
1) acrylic acid/allyl-2-hydroxypropanesulfonic ether;
2) acrylic acid/allyltriethoxysilane ether;
3) acrylic acid/2-acrylamide-2-methyl-1-propanesulfonic acid;
4) acrylic acid/ammonium allyltriethoxysilane/alloxy-2-hydroxypropane-3-sulfonic acid;
5) acrylic acid /methacrylic acid/ammonium, allpolitics(10)sulfate;
6) acrylic acid/2-acrylamide-2-methyl-1-propanesulfonic acid/ammonium allyltriethoxysilane.

8. The method according to claim 7, where the said polymer I is a
1) acrylic acid/allyl-2-hydroxypropanesulfonic ether;
2) acrylic acid/allyltriethoxysilane ether; or
3) acrylic acid/2-acrylamide-2-methyl-1-propanesulfonic acid.

9. The method of claim 8, where the said polymer I is an acrylic acid/allyl-2-hydroxypropanesulfonic ether.

10. The method of claim 8, where the said polymer I is an acrylic acid/allyltriethoxysilane ether.

11. The method of claim 8, where the said polymer I is an acrylic acid /2-acrylamide-2-methyl-1-propanesulfonic acid.

12. The method of claim 8, further including the th in contacting said emulsion with a demulsifying agent.

13. The method according to item 12, further comprising adding a corrosion inhibitor to the above-mentioned liquid hydrocarbon medium or referred to the aquatic environment.

14. The method of claim 8, where the emulsion was heated to a temperature of about 100-300°F.

15. The method according to 14, where this separation mentioned emulsion was carried out in the apparatus for desalting.

16. The method according to clause 15, where n in the formula I is from 1 to 20, and Z in formula I is selected from Na, K, CA and NH4.

17. A method of reducing calcium deposits on surfaces in contact with the aqueous phase, consisting in the separation of the emulsion in the plant for desalination of oil refinery where crude oil containing calcium, is in contact with sequestrants, which represents a carboxylic acid and wash water for the formation of said emulsion comprising detachable calcium complex in the above-mentioned emulsion, where at least part of these detachable calcium complex is separated in the above-mentioned aqueous phase is described in the division where the above-mentioned method includes contacting mentioned detachable calcium complex with water-soluble or water-dispersible polymer having the formula I:

where E represents a repeating fragment remaining after polymerizes and unsaturated compounds ethylene type; R1represents a hydrogen atom or lower (1-C6)-alkyl; G represents a lower (C1-C6)-alkyl or carbonyl; Q represents O or NH; R2represents the lowest (1-C6)-alkyl; replacement lower (1-C6)-alkyl, lower (C1-C6)-alkylsulfonyl acid; -(Et-O)-n, -(iPr-O)-nor -(Pr-O)nwhere n is in the range from about 1 to 100, and R3represents a hydrogen atom or XZ, where X is an anionic radical selected from the group consisting of SO3, RHO3or COO; Z represents a hydrogen atom or hydrogen atoms, or any other water-soluble cationic fragment, which serves as a counterbalance to the valency of the anion to the radical X; F, when present, is a recurring fragment having the formula II:

where X and Z are the same as in formula I, R4represents a hydrogen atom or (C1-C6)-lower alkyl, R5is a replacement alkyl or alkylene having from 1 to 6 atoms, and XZ may be present or not be present; C and d are positive integers, f is a nonnegative integer, and j is 0 or 1.

18. The method according to 17, where the aforementioned crude oil includes himself about 100 ppm and more calcium.

19. The method according to p, which referred to prescribe is a citric acid, and in which the aforementioned detachable calcium complex is a calcium citrate, from about 1 to 300 ppm of the above-mentioned polymer (I) was added to the above aqueous phase, counting on one million parts mentioned aqueous phase, where the said polymer is a representative or representatives selected from the group consisting of
1) acrylic acid/allyl-2-hydroxypropanesulfonic ether;
2) acrylic acid/allyltriethoxysilane ether;
3) acrylic acid/2-acrylamide-2-methyl-1-propanesulfonic acid;
4) acrylic acid/ammonium allyltriethoxysilane/alloxy-2-hydroxypropane-3-sulfonic acid;
5) acrylic acid/methacrylic acid/ammonium, allpolitics(10)sulfate;
6) acrylic acid/2-acrylamide-2-methyl-1-propanesulfonic acid/ammonium allyltriethoxysilane.

20. The method according to claim 19, where the said polymer I is a
1) acrylic acid/allyl-2-hydroxypropanesulfonic ether;
2) acrylic acid/allyltriethoxysilane ether; or
3) acrylic acid/2-acrylamide-2-methyl-1-propanesulfonic acid.

21. The method according to claim 1 where the above-mentioned liquid hydrocarbon medium is a crude oil obtained is left at the place of production of oil, where mentioned stages (a)-(C) is carried out in close proximity to the mentioned place.



 

Same patents:

Treatment process // 2316577

FIELD: petroleum processing.

SUBSTANCE: invention relates to process of treating hydrocarbon stock, in particular to reducing nitrogen level in liquid hydrocarbon stock. Process is characterized by that (a) liquid hydrocarbon stock containing alkylation agent and organonitrogen compounds is brought into contact with acid catalyst at elevated temperature in a first reaction zone to form liquid hydrocarbon stock with reduced content of alkylation agent and organonitrogen compounds having elevated boiling temperatures; and (b) liquid hydrocarbon stock with reduced content of alkylation agent and containing organonitrogen compounds with elevated boiling temperatures is fractioned to remove said organonitrogen compounds.

EFFECT: enabled production of liquid hydrocarbon stock with reduced content of alkylation agent and reduced nitrogen level.

14 cl, 3 dwg

The invention relates to integrated processing of high-temperature pyrolysis condensate fraction homogeneous pyrolysis of saturated hydrocarbons WITH3-C5

The invention relates to removing bromine-reactive hydrocarbon contaminants from aromatic materials through contact of these products with acid active catalyst

FIELD: oil-and-gas production.

SUBSTANCE: invention related to method of diesel fuel refinery and aimed to increase quality of a typical and off-quality fuel by decontamination it out from harmful impurities. Invention consists diesel fuel decontamination method, which includes dosed mixing of row fuel with water, solution cavity treatment and its separation on the fuel and deposits and water in a precipitation tank, before dosed mixing with a row fuel water to be saturated with iron ions till solution get yellow-brown colour with pH>6, solution cavity treatment executed by supersonic sound during its CO2 barbotage with temperature 75-80°C and overburden relatively to solution pressure >0.2 gatm, after that solution treated with light photons with energy 60-70 kkal/mole, passed through magnetic field and forwarded to tank.

EFFECT: invention is also related to diesel fuel decontamination equipment.

13 cl, 1 ex, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of reaction mixture processing, obtained by Fischer-Tropsh process (F-T), which includes synthesis-gas, Fischer-Tropsh hydrocarbons, oxygenates and catalyst particles, claimed method being characterised by including: (a) modification of metal-oxygenate components, contained in reaction mixture, obtained by Fischer-Tropsh process, in hydrothermal reaction zone and (b) influencing with subjected to filtration adsorbent on reaction mixture obtained by Fischer-Tropsh process, in hydrothermal reaction zone, subjected to filtration adsorbent being added into hydrothermal reaction zone.

EFFECT: application of given method allows to reduce formation of depositions on technological equipment.

10 cl, 3 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention includes the primary methanol separation on the hydrophilic ultrafine or superfine fiber up to the residual methanol concentration no more than 250 mg/l of the liquid hydrocarbons, extraction of the methanol from liquid hydrocarbons with water, separation of the water solution of methanol from liquid hydrocarbons, removal of the purified hydrocarbons and water solution of methanol, if necessary the removal of the residual water solution of methanol from liquid hydrocarbons with sorption and following desorption and/or catalytical conversion obtaining hydrocarbons and water.

EFFECT: decrease of the energy consumption and efficiency increase in the process of liquid hydrocarbons purification from water methanol solution.

2 cl, 7 ex, 9 dwg

FIELD: chemistry.

SUBSTANCE: recovered medium is mixed with water in the ejector. It is accompanied with high-pressure water supply to ejector pump nozzle in the line connecting high-pressure system and ejector pump inlet. Thereafter mixed water and recovered agents are drained out through the pipeline to the sedimentation tank. Recovered suspension is collected from the tank through the pipeline connecting suspension layers and ejector pump inlet. Optimal performance of the ejector is ensured by observing the suggested ratios of ejector nozzle diameter, ejector diameter and ejector nozzle length.

EFFECT: higher productivity.

4 dwg, 2 tbl

FIELD: machine building.

SUBSTANCE: invention relates to recovery of fluids, primarily of thickened lubricants. The proposed device comprises a mixer to mix fluid to be recovered with water. The said mixer incorporates an intake chamber, jet pump ejecting nozzle arranged axially symmetric to the aforesaid chamber and including a central and throttling orifices. The intake manifold of ejected flow of the fluid to be recovered is mounted inside the intake chamber perpendicular to its axis, the said manifold being connected to the tank with fluid to be recovered. The intake chamber communicates via confuser with the missing chamber, which in its turn is connected via diffuser with rectilinear transport pipeline connected with a settling tank.

EFFECT: higher efficiency.

2 tbl, 3 dwg

FIELD: organic chemistry.

SUBSTANCE: invention refers to hydrocarbon raw materials decontamination from sulphur compounds and can be applied in oil-processing industry. Described hydrocarbon raw materials decontamination from sulphur and sulphur compounds includes oxidation at contact of hydrocarbon raw materials with process reagent, mixture separation resulted from this contact with decontaminated hydrocarbon raw materials, before oxidation hydrocarbon raw materials are treated with, negative electromagnetic field and after oxidation with oxygen as process reagent hydrocarbon raw materials flow goes heavily stirred water containing reagent in proportions to hydrocarbon raw materials within 1:50. Then mixture flow is dispersed and soothed before separation and additional selection of released gas and sediment. Technological effect is simplification of hydrocarbon raw materials decontamination process.

EFFECT: simplification of hydrocarbon raw materials decontamination from sulphur and sulphur compounds.

5 cl, 1 dwg, 1 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.

EFFECT: reduced consumption of demulsifier at higher degree of desalting, in particular for oils with high level of chlorides.

7 cl, 2 ex

FIELD: oil and gas production.

SUBSTANCE: invention relates to methods of oil cleaning against volatile sulfur-containing compounds. Invention relates to cleaning method of hydrogen sulfide- and mercaptan bearing oil, with receiving of separator oil, including physical cleaning of oil by means of double concentration of removed components in gaseous phase of distillate by rectification and removal after rectification from bottom of towers of liquid phase, directed into separator oil, chemical cleaning of distillate by means of extraction of hydrogen sulfide and mercaptans from partially condensed secondary concentrate by matched extraction processes, desorption and absorption, implemented in apparatus of column at presence of stripping gas and extracted from oil water, where it is also fed reagent, allowing bactericidal activity to sulphate-restoring bacteria and corrosion-inhibiting action, extracted cleaned phase of secondary concentrate is partially directed into separator oil.

EFFECT: method provides for implementation of nonwaste cleaning technology of oil against hydrogen sulfide and light mercaptan, reduction of reagent consumption, excluding of danger of ingress of reaction products into separator oil and marketable tanks of oil.

5 cl, 3 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: process liquids and well products are purified from hydrogen sulphide and organic sulphur compounds by bringing them into contact with a sulphur-removing reagent - aqueous solution of products of reaction of formaldehyde and nitrogen-containing organic bases. The method is distinguished by that, the sulphur-removing reagent also contains an aprotonic dipolar solvent, with the following ratio of reagents, wt. pts: aqueous solution of products of reaction of formaldehyde and nitrogen-containing bases - 100; aprotonic dipolar solvent - 10-40.

EFFECT: simplification of the purification method with increase in its efficiency at the same time and reduced consumption of sulphur-removing reagent.

FIELD: chemistry.

SUBSTANCE: proposed hydrogen sulphide and/or low-molecular mercaptan remover is in form of amino esters with general formula: (R-)nN(-CH2-O-R')m, where R is alkyl, isoalkyl C1-C14 or cyclohexyl, or benzyl, or a bivalent group with formula - CH2-O-CH2-CH2-, bonded to a nitrogen atom of an amino ester, with formation of five-member heterocyclic ring; R' - alkyl, isoalkyl or alkenyl, preferably C1-C4; n=1 or 2, m=3-n. The invention also pertains to the method of purifying oil, water-oil emulsions, oil products, hydrocarbon gases, stratal water and process liquids from hydrogen sulphide and/or low-molecular mercaptans by treating the starting material using the above described remover. The proposed remover and a composition based on it have higher reaction capacity compared to hydrogen sulphide, light mercaptans and provides for their effective neutralisation in aqueous and non-aqueous media at normal and high temperatures (10-90°C and above). The proposed remover also has bactericidal activity towards sulphate reducing bacteria and anti-corrosion activity in hydrogen sulphide-containing media, and can be used as a bactericide-inhibitor of hydrogen sulphide corrosion in oil-field media.

EFFECT: improved properties of the remover.

4 cl, 9 ex

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

FIELD: oil and gas processing.

SUBSTANCE: neutralizer contains 30-60% formalin, 0.1-3% alkali metal (sodium) hydroxide and/or carbonate, 5-35% bactericidal agent, preferably Baktsid, Sontsid, or Sulfan, and tertiary aminoalcohol (triethanolamine and/or methyldiethanolamine) to 100%. Neutralizer may further contain urotropin in amount from 5 to 22%. With such composition, effective neutralizer is characterized by high processability (low freezing temperature) and reactivity, which favors high degree of purification of crude oil, petroleum products, and hydrocarbon gases polluted by hydrogen sulfide and light mercaptans.

EFFECT: enhanced neutralization activity accompanied by bactericidal activity and anticorrosion effect in hydrogen sulfide-containing media.

4 cl, 1 tbl, 15 ex

Treatment process // 2316577

FIELD: petroleum processing.

SUBSTANCE: invention relates to process of treating hydrocarbon stock, in particular to reducing nitrogen level in liquid hydrocarbon stock. Process is characterized by that (a) liquid hydrocarbon stock containing alkylation agent and organonitrogen compounds is brought into contact with acid catalyst at elevated temperature in a first reaction zone to form liquid hydrocarbon stock with reduced content of alkylation agent and organonitrogen compounds having elevated boiling temperatures; and (b) liquid hydrocarbon stock with reduced content of alkylation agent and containing organonitrogen compounds with elevated boiling temperatures is fractioned to remove said organonitrogen compounds.

EFFECT: enabled production of liquid hydrocarbon stock with reduced content of alkylation agent and reduced nitrogen level.

14 cl, 3 dwg

FIELD: petrochemical industry; other industries; methods of production of the hydrogen for the fuel composition.

SUBSTANCE: the invention is pertaining to the method of production of hydrogen for the fuel composition. The method of production of hydrogen for the fuel composition from the hydrocarbon fuel composition includes the following stages: preparation of the hydrocarbon fuel composition, which is produced: i) injection of the liquid hydrocarbon raw including the alkylating agent, in contact with the acid catalyst in the conditions, which are effective for alkylation, at least, of the parts of the hydrocarbon raw, where the liquid hydrocarbon raw additionally includes the aromatic compounds, which are alkylated at the stage of the alkylation; and ii) separation from the stage of the alkylation of the low-boiling fraction containing the hydrocarbons and the aromatic hydrocarbons with the lowered concentration in the capacity of the hydrocarbon fuel composition, transformation of the hydrocarbon fuel composition into the hydrogen and optional injection of the produced hydrogen into the fuel composition. The invention makes it possible to raise efficiency of the production process.

EFFECT: the invention ensures the increased efficiency of the production process.

10 cl, 3 tbl, 3 ex

FIELD: crude oil treatment.

SUBSTANCE: treatment of hydrogen sulfide-containing crude oil before transportation and separation comprises multistep separation of original crude oil followed by dehydration and desalting, flushing with hydrocarbon gas in desorption column, and addition of monomethanolethanolamine (obtained by reaction of monomethanolamine with formaldehyde), and stirring. Flushing is accomplished with hydrogen sulfide-containing gas ensuring weight percentage of hydrogen sulfide in post-flushing oil no higher than 200 ppm. After addition of monomethanolethanolamine, according to invention, up to 10% of fresh washing water is additionally charged. All aforesaid operations are carried out before desalting step.

EFFECT: reduced contents of hydrogen sulfide and water in commercial oil.

1 dwg, 3 tbl

FIELD: oil production, oil refinery and petrochemical industries, particularly for hydrogen sulfide and mercaptan neutralization in hydrocarbon medium with the use of chemical neutralization agents.

SUBSTANCE: hydrogen sulfide and mercaptan neutralizing agent comprises 30-58% by weight of formalin, alkali metal, preferably sodium, hydroxide or carbonate in amount of 0.1-3% by weight, hexamethylenetetramine in amount of 15-25% by weight, remainder is tertiary alkamine, preferably triethanolamine and/or methyldethanolamine. Neutralizing agent in accordance with the second embodiment additionally includes bactericide composition.

EFFECT: increased neutralizing agent efficiency, enhanced manufacturability (low solidification temperature) and reactivity, provision of high hydrocarbon medium (oil, oil product and gaseous hydrocarbon) cleaning of hydrogen sulfide and light-weight mercaptans at room and increased temperatures (of 10-90°C and higher), improved bactericidal activity and corrosion inhibiting effect in hydrogen sulfide mediums, possibility of neutralizing agent usage as bactericide and corrosion inhibitor in oil-field media.

7 cl, 15 ex, 1 tbl

FIELD: crude oil treatment.

SUBSTANCE: to remove hydrogen sulfide and mercaptans, 3-30% solution of urotropin in technical-grade formalin or in formalin/aqueous ammonia is added to crude material in amounts corresponding to 0.8-3.5 mole formaldehyde and 0.009-0.3 mole urotropin per 1 mole hydrogen sulfide and mercaptan sulfur. Reaction is carried out at 15 to 70°C. Method is applicable for oil and gas production and petroleum processing industries.

EFFECT: reduced consumption of reagents at high degree of purification of raw material.

5 cl, 3 tbl

FIELD: crude oil treatment.

SUBSTANCE: to remove hydrogen sulfide and mercaptans, 3-30% solution of urotropin in technical-grade formalin or in formalin/aqueous ammonia is added to crude material in amounts corresponding to 0.8-3.5 mole formaldehyde and 0.009-0.3 mole urotropin per 1 mole hydrogen sulfide and mercaptan sulfur. Reaction is carried out at 15 to 70°C. Method is applicable for oil and gas production and petroleum processing industries.

EFFECT: reduced consumption of reagents at high degree of purification of raw material.

5 cl, 3 tbl

Up!