Tool for removal of hydrogen sulfide and mercaptans from gases, oil, oil, produced water and drilling fluids

 

(57) Abstract:

The invention relates to reagents having the ability to remove hydrogen sulfide and mercaptans from gases, oil, oil, produced water, drilling fluids, and can be used on objects of oil production, refining, petrochemicals for their neutralization by neutralizing biogenic sulfur compounds. The proposed tool is a 70% aqueous solution of 1-hydroxy-2-(1,3-oxazolidin-3-yl)ethane General formula C4H9NO2. The invention provides in comparison with the known means higher serovodorodnoi ability, activity against mercaptans, good compatibility with oil, the independence of action of temperature, pH, the presence of impurities. The proposed tool is also characterized by the absence of corrosive action, and a high rate of interaction with a removable substances. 1 PL.

The invention relates to substances which are able to neutralize the oil production facilities, oil refining, petrochemistry from sulfur compounds, in particular to substances that can be applied for purification of petroleum, natural or tennage the East connections and can find application in the oil and gas, petrochemical and other industries.

One of the serious problems of the modern oil processing industries is the contamination of the oil-bearing strata by biogenic sulfide and mercaptans. Hydrogen sulfide and mercaptans, being toxic and corrosive substances, sometimes become an obstacle to the development of mining, oil and gas production and transportation and further processing. Cleaning of oil production facilities and processing from sulfur compounds is carried out at different stages of the process. Typically, cleaning raw materials are organized separately for oil and gas in a variety of ways using different reagents.

Purification of gases.

Known /1. Cole, A. L., Rosenfeld F. C. “gas Purification”, M.: Izd. The subsoil, 1966/ liquid absorbents for gas purification from hydrogen sulfide consisting of the amino compounds and water in the following ratios, wt%:

Monoethanolamine 15-20

Water The Rest

If that describes the absorber has a high capacity (0.25 to 0.45 mol/mol IEA) hydrogen sulfide and a sufficient depth of treatment, it has sevana hard to remove by-products of the interaction with hydrogen sulfide.

To a lesser extent the mentioned disadvantages inherent in the adsorption solutions based on the tertiary amino compounds, as tretamine unusual reactions chemical interaction with hydrogen sulfide.

However, the selectivity for hydrogen sulfide is not achieved and in this case, since the complexing properties of tretamine close against hydrogen sulfide, carbon dioxide and sulfur gases.

Known absorption solution based on the tertiary amine - methyldiethanolamine (hereinafter MDEA) /2. Khabibullin P. P., Rogozin Century. And., Vysheslavtsev Y. F. Modern methods of cleaning gases from acid components, M., 1988. Survey information./, contains, wt%:

MDEA 30

Water The Rest

The process is carried out by ozonation of the purified gas through the adsorption solution. The hydrogen sulfide content was decreased from 30 to 5 mg/m3the carbon dioxide content was also decreased from 30 to 5 mg/m3.

The advantage of the described adsorption composition compared to the same based on triethanolamine - lower molecular weight, which causes an increase in the capacity of sorbed gases.

The main disadvantages of the described absorption solution awosanya to mercaptans.

Purification of produced water.

Neutralization of hydrogen sulfide in produced water at current and capital repair of wells is known reagents, in particular by chloramine-B /4. RD 39-3-938-83. Instruction on application of the method of neutralization of hydrogen sulfide in produced water used for well killing, 1983/.

The disadvantages of chloramine B are relatively low servedobednitsa capacity (100 mg H2S per gram of reagent), corrosivity due to the high content of chlorine.

Drilling mud cleaning.

Special requirements to the neutralizers of hydrogen sulfide in drilling fluids, because the reagents used in these facilities, not only to free the solution from the hydrogen sulfide, but not to change while the rheological characteristics of the mud.

Most suitable for neutralization of hydrogen sulfide in drilling fluids organic compounds that do not affect viscosity and structural-mechanical properties of solutions. Known reagent T-66 /5. THE 38-10-3243-74, Sputnik drillers” K. I., Ganesan, M.: Nedra, 1990/ used as a neutralizer of hydrogen sulfide in drilling fluids. On the technical essence of the prevailing hydrogen in a chemical compound. The amount of bound H2S ranges from 25 to 100 mg per 1 g of reagent depending on the temperature and pH of the environment.

The disadvantages of this reagent are ineffective against mercaptans, low capacity for hydrogen sulfide, reducing the absorption capacity in the presence of the dispersed phase by 43% /6. Rusaev A. A., K. Surkova I. Comparative evaluation of the efficacy of sulphide scavengers in clay drilling fluids. Sat. proceedings of the 5th national conference on physics, chemistry, technology of production and application of drilling fluids, disperse systems and cement slurries, Kiev, Naukova Dumka, 1981, 1 o'clock, p. 168-169/.

Petroleum refining.

Neutralization of hydrogen sulfide in crude oil is produced simultaneously with the neutralization of the produced water in the oil or later, prior to refining processes described above reagents. Closest to the claimed means of the reagent T-66. The virtue of the known reagent in that the reagent is of organic nature better penetrates into the oil due to dissolution. Disadvantages reagent T-66 - low servedobednitsa capacity, inefficient absorption of mercaptans.

Purification of the oil.

Kataliticheskogo oxidation /5. Sharipov A. H., kabyles A. A., Nigmatullin C. R. Clean fuels and liquefied gases from mercaptans and sulfides, Ufa, 1999/. These methods can reduce the sulfur content to hundreds of ppm. Such values do not satisfy the increased current requirements for fuels.

These disadvantages of the known processes for purifying gases and liquids from the sulfur compounds are removed by the application as a means for removal of hydrogen sulfide and mercaptans aqueous solution of 1-hydroxy-2-(1,3-oxazolidin-3-yl)ethane, then GOUDA, the General formula C4H9NO2.

Get GOADE by the interaction of formaldehyde and monoethanolamine at a temperature of 0-40°C for 20-24 hours in the presence of a catalyst to the alkaline nature. The resulting aqueous solution of GOUDA use without further processing.

The process of gas purification from hydrogen sulfide and mercaptans performed by ozonation of the purified gas through a 70% aqueous solution of GOUDA at temperatures of 0-100°C, atmospheric or elevated pressure, the rate of gas supply 10-200 h-1. In the process of cleaning gases reduced hydrogen sulfide concentration to 1-2 mg/m3, reducing the concentration of mercaptans to containest the claimed means for removal of hydrogen sulfide and mercaptans from gases in selectivity with respect to hydrogen sulfide and mercaptans, which allows you to extract only the specified connection and thereby reduce the flow rate of the reagent-absorber.

The effectiveness of the proposed tools is illustrated by examples of 1.2. When neutralizing the produced water and the reactivation of wells using GOUDA allows to reduce the consumption of means for removal of sulfur compounds due to the higher serovodorodsoderzhashchij ability GOODE (150 mg H2S 1 g of product) and good compatibility aqueous solution of GOUDA with formation waters. The advantages of the proposed drug is also that GOADE not exhibit corrosive action.

The use of the proposed drug, GOUDA for neutralization of hydrogen sulfide and mercaptans in drilling fluids allows you to remove sulfur compounds with greater efficiency than known means, due to the higher serovodorodsoderzhashchij ability and high ability to absorb mercaptans. Advantages of GOUDA are also good compatibility with any composition of drilling fluids, independent of its action on temperature and pH of the medium, as well as anticardium action. The use of GOUDA does not change R is omashu GOUDA is carried out by treating the oil with an aqueous solution of GOUDA at temperatures of 0-100°C atmospheric or pressure. The use of the proposed drug to neutralize the oil from sulfur compounds makes it possible to decrease concentrations of hydrogen sulfide and mercaptans to individual values in ppm, and the efficiency of the process is not dependent on pH, temperature, presence of mechanical impurities. Higher efficiency of GOUDA compared with the known means of cleaning oil from sulfur compounds due to the chemical nature of GOUDA, its ability to bind sulfur compounds with high capacity - up to 150 mg/m3, good compatibility with oil.

The efficacy of the proposed drug for the removal of hydrogen sulfide and mercaptans from petroleum is illustrated by examples 3-4.

The use of the proposed drug, GOUDA for cleaning oil from sulfur compounds allows to achieve a desired quality of fuels for all categories of petroleum products. The process of removing hydrogen sulfide and mercaptans from petroleum products is carried out by treating the raw material with an aqueous solution of GOUDA at atmospheric or elevated pressure, temperature 0-100°C. the application of GOUDA it is possible to reduce the hydrogen sulfide content to hundredths of a ppm, with whom I was cleaning out the different categories of oil products is illustrated by examples 6-8.

The invention is illustrated in the examples.

Example 1. The removal of hydrogen sulfide from hydrocarbon gas.

In the cylinder containing 100 ml of absorbing solution composition:

1-Hydroxy-2-(1,3-oxazolidin-3-yl)ethane 70%

Water The Rest

missed the gas containing

Hydrocarbons 90%

The Hydrogen Sulfide 5%

Carbon dioxide 5% vol.

At the outlet of the cylinder was controlled by the composition of the gas. The content of hydrocarbons and carbon dioxide were determined chromatographically, as the source gas. The hydrogen sulfide content in the purified gas was determined using a gas analyzer “RIKEN KEIKI” with an accuracy of up to 0.5 mg/m3. The amount of the missed gas 134,7 l, the content of hydrogen sulfide in this volume 6,74 l (10,225 g).

The composition of the gas at the exit after cleanup:

Hydrocarbons 94,74%

Carbon dioxide, gas 5,26%

The hydrogen sulfide 1.5 mg/m3

Example 2. Removal of sulfur compounds from natural gas.

Is similar to example 1. The results are shown in the table.

Example 3. The removal of hydrogen sulfide from crude oil.

In a flask equipped with stirrer, were placed 100 g of oil containing 0.18 g of hydrogen sulfide and yecenia 5 minutes then analyzed the processed oil to hydrogen sulfide. The analysis showed the absence of hydrogen sulfide.

Example 4. Removal of sulfur compounds from crude oil.

Is similar to example 3. The results are shown in the table.

Example 5. Neutralization of hydrogen sulfide in the formation water.

A sample of produced water volume of 100 ml with established content of hydrogen sulfide 0.2 g were treated in the flask 1.9 ml of a 70% aqueous solution of GOUDA for 5 minutes, then analyzed the water content of hydrogen sulfide. The analysis showed the absence of hydrogen sulfide in the sample.

Examples 6, 7, 8. Removal of sulfur compounds from petroleum products.

A sample of the oil was shaken in a separating funnel with a given amount of an aqueous solution of GOUDA for 10-30 minutes. The sample was passed to separation of the phases. In the layer of oil was determined by the content of hydrogen sulfide and mercaptans. The results are shown in the table.

Thus, the claimed means of GOUDA able to effectively neutralize the hydrogen sulfide and mercaptans in the gas and formation waters, drilling fluids, petroleum and petroleum products, i.e. GOUDA has a wide range of actions, in other words, is imeneniya on various objects of oil and gas production and processing.

The experimental conditions: atmospheric pressure, room temperature, a processing time of 0.5 to 2 hours, 70% aqueous solution of GOUDA.

Tool for removal of hydrogen sulfide and mercaptans from gases, oil, oil, produced water and drilling fluids, characterized in that as a means of removal of hydrogen sulfide and mercaptans using 70% aqueous solution of 1-hydroxy-2-(1,3-oxazolidin-3-yl)ethane General formula C4H9NO2.



 

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