RU2533494C1 - Reagent for absorbing hydrogen sulphide and light mercaptan (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: reagent-absorber includes a substituted derivative of triazine, and namely 1,3,5-tri-(hydroxymethyl)-hexahydro-S-triazine, or 1,3,5-tri-(2-hydroxyethyl)-hexahydro-S-triazine, or their mixture, a quaternary ammonium compound, and alkylphosphites of N-alkylammonium chloride - amphicore.

EFFECT: invention makes it possible to create a commercially available reagent-absorber of hydrogen sulphide and light mercaptans, extend an assortment of the known absorbers.

9 cl, 30 ex

Description

The invention relates to the field of petrochemistry, namely to neutralize hydrogen sulfide and light mercaptans in aqueous, hydrocarbon, and also in water-hydrocarbon emulsion media with chemical reagents and can be used in the oil and gas, oil and gas processing and petrochemical industries.

The invention relates to a reagent-absorber-neutralizer of hydrogen sulfide and light mercaptans for quick and effective reduction of their content, including in the produced oil.

The presence of hydrogen sulfide in the reservoir oil of a significant part of Russian deposits of both relict and biogenic, as well as mercaptans, determines a number of serious complications in the extraction and refining of oil, associated with their high corrosiveness and toxicity, is one of the serious problems of the modern oil production and refining industry , leads to an increase in the content of sulfur compounds in oil and petroleum products.

Quickly and effectively reduce the content of hydrogen sulfide and light mercaptans due to their binding and transfer to safe non-volatile compounds allows the use of chemical absorbers-neutralizers. In addition, the use of such absorbers requires the least capital investment. The creation of an effective commercially available absorber of hydrogen sulfide and mercaptans in a stable commercial form and at low temperatures for oils with a high content of hydrogen sulfide and light mercaptans is an urgent problem.

Absorbers and methods are known for using them, where compositions based on triazine, its derivatives, their mixtures are used to remove hydrogen sulfide and light mercaptans (WO No. 2009/027721, publ. 05.03.2009; RU No. 2080909, publ. 06/10/1997; US No. 5554349, publ. 09/10/1996; US No. 5128049, publ. 07/07/1992; EP No. 2267098, publ. 29.12.2010). Despite their high selectivity with respect to H ₂ S and mercaptans, the irreversibility of the reaction, the required purification depth, the absence of hazardous effluents, the disadvantage of these neutralizers is their low absorption capacity with respect to hydrogen sulfide (4.5-6 g / g hydrogen sulfide). Often a significant drawback is the long time required to achieve a given depth of purification from hydrogen sulfide.

Mercaptan scavengers are known, in addition to H ₂ S, described in the patent (US No. 7264786, published October 27, 2005) using substituted triazine derivatives with quaternary amino groups, morpholines, piperazines, amino alcohols, amino oxides or polyamines. The disadvantage of such absorbers is the high cost of raw materials and target products and its low manufacturability due to the high viscosity of commodity forms.

The closest in technical essence and the achieved effect are absorbers used in the method of processing gaseous and liquid hydrocarbons according to the patent (US No. 5744024, publ. 04/28/1998) containing a substituted triazine derivative, in combination with a quaternary ammonium compound, taken in a ratio of 10 : 0.1 to 1: 1. The results described in the prototype were obtained for the vapor phase, and kerosene was used as a liquid hydrocarbon, which was saturated with hydrogen sulfide.

However, this absorber, when tested on sulphurous oils, shows insufficient absorption efficiency (Table 2), does not allow to obtain the required depth of effect (in 2 hours a high result is not achieved), as required by the conditions dictated by existing oil preparation technologies.

The objective of the invention is the creation of an effective, commercially available reagent-absorber of hydrogen sulfide and light mercaptans, expanding the range of known absorbers.

The problem is solved by the proposed reagent-absorber of hydrogen sulfide and light mercaptans (option 1), which is a composition comprising a substituted triazine derivative, a quaternary ammonium compound and a solvent additionally containing alkylphosphites of N-alkylammonium chloride - Amphicore, and 1.3 as a triazine derivative , 5-tri- (hydroxymethyl) -hexahydro-S-triazine, in the following ratios of components, wt.%:

1,3,5-Tri- (hydroxymethyl) -hexahydro-S-triazine  17-21 Quaternary ammonium compound  5-10 Alkylphosphites N-alkylammonium chloride - Amfikor  5-10 Solvent  Rest

The problem is also solved by the proposed reagent-absorber of hydrogen sulfide and light mercaptans (option 2), which is a composition comprising a substituted derivative of a triazine, a quaternary ammonium compound and a solvent additionally containing alkylphosphites of N-alkylammonium chloride - Amfikor, and 1 as a derivative of triazine. 3,5-tri- (2-hydroxyethyl) -hexahydro-S-triazine, in the following ratios of components, wt.%:

1,3,5-Tri- (2-hydroxyethyl) -hexahydro-S-triazine 40-50 Quaternary ammonium compound 5-10 Alkylphosphites N-alkylammonium chloride - Amfikor 5-10 Solvent Rest

The problem is also solved by the proposed reagent-absorber of hydrogen sulfide and light mercaptans (option 3), which is a composition comprising a substituted derivative of a triazine, a quaternary ammonium compound and a solvent additionally containing alkylphosphites of N-alkylammonium chloride - Amfikor, and mixture 1 as a derivative of triazine , 3,5-tri- (hydroxymethyl) -hexahydro-S-triazine and 1,3,5-tri- (2-hydroxyethyl) -hexahydro-8-triazine, taken in a ratio of 1.0: (1.1-4 , 55), with the following ratios of components, wt.%:

A mixture of 1,3,5-Tri- (hydroxymethyl) -hexahydro-S-triazine and

1,3,5-tri- (2-hydroxyethyl) -hexahydro-8-triazine  25-35 Quaternary ammonium compound  5-10 Alkylphosphites N-alkylammonium chloride - Amfikor  5-10 Solvent  Rest

As the quaternary ammonium compound, for example, dioctyldimethylammonium chloride or didecyldimethylammonium chloride or benzyldiodecyldimethylammonium chloride, benzyl cocodimethylammonium chloride can be used.

Amphicor corrosion inhibitor, a water-soluble salt of derivatives of nitrogen- and phosphorus-containing compounds, is used as alkylphosphites of N-alkylammonium chloride.

The solvent is aqueous methanol or water.

The presence of a salt of alkylphosphites of N-alkylammonium chloride - Amfikor, as well as the use of 1,3,5-tri- (hydroxymethyl) -hexahydro-S-triazine, or 1,3,5-tri- (2-hydroxyethyl) as a substituted triazine derivative -hexahydro-S-triazine, or mixtures thereof, taken in a ratio of 1.0: (1.1-4.55), allows to achieve the absorption capacity of the proposed composition (options) 90-100%, to obtain the necessary depth of effect for significantly sulphurous oils in 2-6 hours, get a commercially available absorber, effective and stable at temperatures up to -30 ° C, expand asso raw materials used.

According to the invention, a reagent-absorber of hydrogen sulfide and light mercaptans (options) is obtained by synthesizing a substituted triazine derivative by the interaction of low molecular weight aldehyde (preferably formaldehyde) and an aminating agent, taken in the ratio 1: (1.8 ÷ 2.2) for the case of aqueous ammonia or 1: (0.8 ÷ 1.2) for the case of alkanoamines (preferably monoethanolamine) at a temperature not exceeding 60 ° C, and subsequent mixing of the resulting product with a quaternary ammonium compound (in an amount of 5-10 wt.%), And adding a water solution to the mixture of their alkylphosphites N-alkylammonium chlorides (in the amount of 5-10 wt.%).

As a low molecular weight aldehyde, formaldehyde (GOST 1625-89) or acetaldehyde (TU 38.402-62-148-94, as amended 1-3) is used, more preferably formaldehyde or paraform (TU 6-09-141-03-89).

As the aminating agent, mono- or dialkano-lamines are used, most preferably monoethanolamine (TU 2423-159-00203335-2004), as well as aqueous ammonia (GOST 3760-79).

When the amino alcohol is monoethanolamine, and formaldehyde is used as the aldehyde, the reaction product is mainly 1,3,5-tri- (2-hydroxyethyl) -hexahydro-S-triazine (compound II) and the reaction is carried out according to patent (RU No. 2080909, publ. 10.06.1997); when using aqueous ammonia, the reaction product is 1,3,5-tri- (hydroxymethyl) -hexahydro-S-triazine (compound I), the reaction is carried out according to (Organikum: workshop on organic chemistry / 15th ed., translation into Russian , Mir, 1979.- t.2, p.59.).

The preferred molar ratio of amino alcohol: aldehyde is 1: 1, aqueous ammonia: aldehyde is 2: 1.

As the quaternary ammonium salt, dioctyl dimethyl ammonium chloride (CAS No. 5538-94-3), didecyldimethyl ammonium chloride (CAS No. 7173-51-5), benzyldodecyldimethyl ammonium chloride (CAS No. 8001-54-5), benzyl cocodimethyl ammonium chloride 34 (CAS -2).

Alkylphosphites of N-alkylammonium chloride are water-soluble salts of derivatives of nitrogen and phosphorus compounds, are produced under the trade name Amfikor according to (TU 39-12966038-004-95).

Methanol is used according to (GOST 2222-95).

The inventive neutralizing agent of hydrogen sulfide and light mercaptans (options) is a uniform transparent liquid from colorless to light brown in color with a density at 20 ° C 0.990 ÷ 1.010 g / cm ³ , kinematic viscosity at 20 ° C no more than 100 mm ² / s , pour point no higher than minus 30 ° C.

Distinctive features of the inventive absorbent reagent (options) is the presence of salt - alkylphosphite N-alkylammonium chloride, known as a corrosion inhibitor Amfikor. However, its properties as an absorber of hydrogen sulfide and light mercaptans are not known. Our studies have shown that Amphicore has a weak absorption capacity. Its effectiveness lies in the range up to 10%. The high absorption capacity of the claimed composition with his participation can be explained by the effect of synergism in the three-component system.

Analysis of the known technical solutions showed the absence of objects similar to the claimed one according to the totality of features, with the presence of the above properties, which allows us to conclude that the proposed solutions meet the criteria of "novelty" and "inventive step".

To prove the compliance of the proposed solutions to the criterion of "industrial applicability" we give examples of specific performance.

Example 1

Obtaining 1,3,5-tri- (hydroxymethyl) -hexahydro-S-triazine (compound I).

Compound I is prepared according to the method described in (Organicum: Workshop on Organic Chemistry / 15th ed., Translation into Russian, Mir, 1979. - vol. 2, p. 59), from aqueous ammonia and formaldehyde taken in molar 2: 1 ratio.

420.0 g of 25% ammonia water are charged into the reactor with continuous stirring and cooling of the reaction mixture, then 487.0 g of formaldehyde (37% form) is slowly added. They monitor the temperature regime - the temperature should not exceed 60 ° C. After the introduction of formaldehyde is stirred for another 30 minutes. Get 22% aqueous solution of compound I.

Example 2

Obtaining 1,3,5-tri- (2-hydroxyethyl) -hexahydro-S-triazine (compound II).

Compound II is obtained according to the method described in patent RU No. 2080909 from monoethanolamine and formaldehyde taken in a 1: 1 molar ratio.

420.0 g of monoethanolamine are charged into the reactor with continuous stirring and cooling of the reaction mixture, then 810.0 g of formaldehyde (37% form) is slowly added. They monitor the temperature regime - the temperature should not exceed 60 ° C. After the introduction of formaldehyde is completed, it is stirred for another 30 minutes, 40.0 g of methanol are added to the reaction mixture, and a 50% solution of target compound II in aqueous methanol is obtained.

Example 3

Obtaining 1,3,5-trimethyl-hexahydro-8-triazine (compound III) of the prototype.

Compound III is obtained by the method described in the patent (US No. 5744024, publ. 04/28/1998) from monomethylamine (according to TU 6-02-639-87) and formaldehyde taken in a 1: 1 molar ratio.

310 g of monomethylamine (40% aqueous solution) were charged to the reactor, while 191 g of formaldehyde (63%) was slowly added while stirring and cooling the reaction mixture. They monitor the temperature regime - the temperature should not exceed 60 ° C. After the introduction of formaldehyde is stirred for another 30 minutes. A 34.4% solution of target compound III in water is obtained.

Example 4 (prototype).

With constant stirring, a mixture of 95.0 g of the product obtained in Example 3 and 5.0 g of benzyl cocodimethyl ammonium chloride is prepared. Stirred at a temperature of 20 ° C for 30 minutes. A product is obtained containing 32.6 g of compound III and 5.0 g of a quaternary ammonium salt in water.

Example 5

With constant stirring, a mixture is prepared from an aqueous solution of compound I, containing 20.9 g of compound I, and 5.0 g of benzyldodecyldimethylammonium chloride, is stirred at a temperature of 20 ° C for 30 minutes.

Example 6

A composition is prepared from an aqueous solution of compound I, containing 20.46 g of compound I, didecyldimethylammonium chloride in an amount of 5.0 g, then N-alkylammonium chloride-Amphicor alkylphosphite is introduced in an amount of 2.0 g, stirred at a temperature of 20 ° C for 30 minutes.

Example 7-9

Prepare the composition according to example 6, changing the amount of alkylphosphite N-alkylammonium chloride - 5.0 g, 7.0 g, 10.0 g for examples 7, 8, 9, respectively.

Example 10

With constant stirring, a mixture is prepared from an aqueous solution of compound I containing 19.8 g of compound I and 10.0 g of benzyldodecyldimethylammonium chloride. Stirred at a temperature of 20 ° C for 30 minutes.

Example 11

A composition is prepared containing 18.7 g of compound I, 10.0 g of didecyldimethylammonium chloride, then 5.0 g of N-alkylammonium chloride-Amphicor alkylphosphite is added, 5.0 g is stirred at 20 ° C for 30 minutes. The solvent is water.

Example 12, 13.

The composition of Example 11 was prepared by changing the amount of N-alkylammonium chloride alkylphosphite to 7.0 g and 10.0 g for Examples 12 and 13, respectively.

Example 14

With constant stirring, a mixture is prepared from a water-methanol solution of compound II containing 47.5 g of compound II and 5.0 g of benzyldodecyldimethylammonium chloride. Stirred at a temperature of 20 ° C for 30 minutes.

Example 15

A composition is prepared from a water-methanol solution of compound II containing 46.5 g of compound II, benzyl dodecyldimethyl ammonium chloride in an amount of 5.0 g, then N-alkyl ammonium chloride-Amphicor alkyl phosphite in an amount of 2.0 g is introduced, stirred at a temperature of 20 ° C in within 30 minutes.

Example 16-18.

Prepare the composition according to example 15, changing the amount of alkyl phosphite N-alkylammonium chloride - 5.0 g, 7.0 g, 10.0 g for examples 16, 17, 18, respectively.

Example 19

With constant stirring, a mixture is prepared from a water-methanol solution of compound II containing 19.8 g of compound II and 10 g of benzyldodecyldimethylammonium chloride. Stirred at a temperature of 20 ° C for 30 minutes.

Example 20

A composition is prepared containing compound II in an amount of 42.5 g, didecyldimethylammonium chloride in an amount of 10.0 g, then N-alkylammonium chloride-Amphicor alkylphosphite is introduced in an amount of 5.0 g, stirred at a temperature of 20 ° C for 30 minutes.

Example 21, 22.

The composition of Example 20 is prepared by changing the amount of N-alkylammonium chloride alkylphosphite to 7.0 g and 10.0 g for Examples 21 and 22, respectively.

Example 23

With constant stirring, a mixture is prepared containing 10.45 g of compound I and 23.75 g of compound II (mass ratio 1: 2.3), a quaternary ammonium salt of dioctyl dimethyl ammonium chloride is added in an amount of 5.0 g, mixed at a temperature of 20 ° C within 30 minutes. The solvent is aqueous methanol.

Example 24

Prepare the composition according to example 23 (maintaining the ratio of products I and II), changing the amount of Quaternary ammonium salt - 10.0 g

 Example 25

With constant stirring, a composition of 9.35 g of compound I and 21.25 g of compound II (mass ratio 1: 2.3) is prepared, a quaternary ammonium salt of dioctyl dimethyl ammonium chloride is added in an amount of 10.0 g, then N-alkyl ammonium alkyl phosphite is introduced chloride - Amphicore in the amount of 5.0 g, stirred at a temperature of 20 ° C for 30 minutes. The solvent is aqueous methanol.

Example 26

With constant stirring, a composition is prepared from: 8.8 g of compound I, 20.0 g of compound II (mass ratio 1: 2.3), 10.0 g of dioctyldimethylammonium chloride, 10.0 g of N-alkylammonium chloride alkylphosphite.

Example 27

With constant stirring, a composition is prepared from: 12.46 g of compound I, 14.17 g of compound II (mass ratio 1: 1.1), 10.0 g of dioctyldimethylammonium chloride, 5.0 g of N-alkylammonium chloride alkylphosphite.

Example 28

With constant stirring, a composition is prepared from: 11.73 g of compound I, 13.33 g of compound II (mass ratio 1: 1.1), 10.0 g of dioctyldimethylammonium chloride, 10.0 g of N-alkylammonium chloride alkylphosphite.

Example 29

With constant stirring, a composition is prepared from: 6.23 g of compound I, 28.33 g of compound II (mass ratio 1: 4.55), 10.0 g of dioctyldimethylammonium chloride, 5.0 g of N-alkylammonium chloride alkylphosphite.

Example 30

With constant stirring, a composition of 5.87 g of compound I and 26.7 g of compound II (mass ratio 1: 4.55) is prepared, a quaternary ammonium salt of dioctyl dimethyl ammonium chloride is added in an amount of 10.0 g, then N-alkyl ammonium alkyl phosphite is introduced chloride - Amfikor in the amount of 10.0 g, stirred at a temperature of 20 ° C for 30 minutes. The solvent is aqueous methanol.

The compositions of the compositions according to examples 1-30 are shown in table 1.

The resulting compositions are tested on oil from the Yuzhno-Nurlatskoye field containing hydrogen sulfide (1290 ppm). Determinations are carried out when dosing the reagent in oil in an amount multiple of the content of dissolved hydrogen sulfide. In all examples, the ratio of H ₂ S: absorber is 1: 4 (4 g of reagent per 1 g of H ₂ S). The processed oil sample is thoroughly shaken to ensure uniform distribution of the reagent in the oil and placed on the platform of a universal shaker, heated to a temperature of 40 ° C. The oscillation frequency of the platform is about 200 min ^-1 .

The determination of hydrogen sulfide content in oil is carried out in accordance with MI 2862-2004 "Measurement of the mass concentration of hydrogen sulfide in crude oil." The calculation of the effectiveness of the reagent is performed using the formula 1:

$$Z\left(\%\right)=\frac{C_{\mathrm{and}\mathrm{from}x}-C_i}{C_{\mathrm{and}\mathrm{from}x}}\mathrm{one\; hundred}\left(\mathrm{one}\right)$$

where: C _Ref - hydrogen sulfide content in the original oil;

C _i - hydrogen sulfide content in the treated oil scavenger after i hours.

The proposed composition has a high absorbing effect in the claimed concentration ranges of the components.

The absorption capacity of compositions without an Amfikor component has lower values than in the presence of Amfikor. So, the absorption capacity of the composition according to example 5 is 79/75/84, according to example 14 is 79/84/86 after 2/4/6 hours, respectively, while the absorption capacity of the composition in the presence of Amphicore reaches 100% (for examples 9 , 13, 18, 20, 21, 22, 25-30).

Concentrations below the stated do not improve the absorption efficiency (examples 4, 13), and above the stated concentration ranges do not improve the effect, but lead to a rise in the cost of the reagent. For example, the use of Amphicor below the declared concentration does not allow to achieve high values of absorption capacity (79/85/86 (example 6) and 81/85/87 (example 15) after 2/4/6 hours, respectively).

You can also see that the inventive reagent-absorber (options) have a higher efficiency compared to the prototype of example 4 (79/85/86 after 2/4/6 hours, respectively).

Achieving a high effect occurs after two hours for oils with a high content of hydrogen sulfide (700 ppm or more).

Using the 1,3,5-tri- (hydroxymethyl) -hexahydro-S-triazine and 1,3,5-tri- (hydroxyethyl) -hexahydro-S-triazine compounds and mixtures thereof as substituted triazine derivatives in the composition of the reagents To absorb hydrogen sulfide and light mercaptans, it expands the range of used raw materials, allows to reduce the cost of the produced reagent, and the introduction of Amfikor into the composition of the commercial product improves its effectiveness, making the reagent promising on the market of hydrogen sulfide and light mercaptan absorbers.

Claims (9)

1. A reagent for the absorption of hydrogen sulfide and light mercaptans, which is a composition comprising a substituted triazine derivative, a quaternary ammonium compound and a solvent, characterized in that it further contains N-alkylammonium chloride-Amphicor alkylphosphites, and 1,3,5 are used as a triazine derivative -tri- (hydroxymethyl) -hexahydro-S-triazine, in the following ratios of components, wt.%:
1,3,5-Tri- (hydroxymethyl) -hexahydro-S-triazine - 17-21,
Quaternary ammonium compound - 5-10,
Alkylphosphites of N-alkylammonium chloride - Amfikor - 5-10,
Solvent - Else. 2. The reagent according to claim 1, where dioctyldimethylammonium chloride, didecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride and benzyl cocodimethylammonium chloride are used as a quaternary ammonium compound. 3. The reagent according to claim 1, wherein aqueous methanol or water is used as the solvent. 4. The reagent for the absorption of hydrogen sulfide and light mercaptans, which is a composition comprising a substituted triazine derivative, a quaternary ammonium compound and a solvent, characterized in that it further contains N-alkylammonium chloride alkylphosphites - Amfikor, and 1,3,5- as a triazine derivative tri- (2-hydroxyethyl) -hexahydro-S-triazine, in the following ratios of components, wt.%:
1,3,5-Tri- (2-hydroxyethyl) -hexahydro-S-triazine - 40-50,
Quaternary ammonium compound - 5-10,
Alkylphosphites of N-alkylammonium chloride - Amfikor - 5-10,
Solvent - Else. 5. The reagent according to claim 4, where dioctyldimethylammonium chloride, didecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride and benzyl cocodimethylammonium chloride are used as a quaternary ammonium compound. 6. The reagent according to claim 4, where aqueous methanol or water is used as the solvent. 7. A reagent for the absorption of hydrogen sulfide and light mercaptans, which is a composition comprising a substituted triazine derivative, a quaternary ammonium compound and a solvent, characterized in that it further contains N-alkylammonium chloride-Amphicor alkylphosphites, and a mixture of 1,3, is used as a triazine derivative. 5-tri- (hydroxymethyl) -hexahydro-S-triazine and 1,3,5-tri- (2-hydroxyethyl) -hexahydro-S-triazine, taken in a mass ratio of 1.0: (1.1-4.55 ), with the following ratios of components, wt.%:
A mixture of 1,3,5-tri- (hydroxymethyl) -hexahydro-S-triazine and
1,3,5-tri- (2-hydroxyethyl) -hexahydro-S-triazine - 25-35,
Quaternary ammonium compound - 5-10,
Alkylphosphites of N-alkylammonium chloride - Amfikor - 5-10,
Solvent - Else. 8. The reagent according to claim 7, where dioctyldimethylammonium chloride, didecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride and benzyl cocodimethylammonium chloride are used as a quaternary ammonium compound. 9. The reagent according to claim 7, where aqueous methanol or water is used as the solvent.