The purification method of crude oil, gas condensate from hydrogen sulfide and mercaptans

 

(57) Abstract:

The invention relates to petrochemistry, in particular to methods of deodorizing cleaning oils and condensates and mixtures of hydrogen sulfide and mercaptans, and can be used in the oil and gas industry. Cleaning is performed by oxidation of the raw material oxygen, taken in an amount of 1.1 to 1.6 mol per 1 mol of hydrogen sulfide and mercaptan sulfur, at a temperature of 10-65oC and a pressure of 0.3 to 3 MPa in the presence as catalyst of a secondary or tertiary alkylamine or tertiary alkanolamine, or mixtures thereof in an amount of 0.01-0.2 wt. %. As secondary and tertiary alkylamine mostly use di-, trialkylamine C1-C4and as tertiary alkanolamine - triethanolamine, methyldiethanolamine or mixtures thereof. When cleaning the raw materials containing the mercaptan and hydrogen sulfide sulfur in the ratio of sr:shmore than 1 in oil or condensate pre-enter the elemental sulfur, the amount of which is calculated by the formula

< / BR>
where SRand SH- the content of mercaptan and hydrogen sulfide sulfur in the feedstock, respectively, by weight. %; 1,7 - stoichiometric reaction coefficient demarcation enter the complex with ferric disodium salt of ethylenediaminetetraacetic acid or a complex of divalent cobalt with pyrophosphate in amount of 0.05 to 3.0 g per 1 ton of oil. The method allows to significantly improve the degree of purification of raw materials from mercaptans while maintaining the degree of purification from hydrogen sulfide at a high level, and to expand the range of the used catalysts. 4 C.p. f-crystals.

The invention relates to petrochemistry, in particular to methods of deodorizing cleaning sulfur crude oil, condensates and mixtures of hydrogen sulfide, mercaptans, and can be used in the oil and gas industry.

Known purification method of crude oil, gas condensate from hydrogen sulfide and mercaptans by processing the feedstock effective amount of hexamethylenetetramine at a temperature of 100-350oF. an effective amount of hexamethylenetetramine is directly proportional to the concentration of hydrogen sulfide and mercaptans in the feedstock and is from 10 to 10000 ppm (U.S. Pat. USA 5213680, 1993).

The disadvantages of this method are the low degree of purification of the raw materials from hydrogen sulfide and mercaptans and significant energy consumption due to the necessity of carrying out the process at elevated temperatures, because of low reactivity of hexamethylenetetramine in relation to hydrogen sulfide and mercaptans at ordinary temperatures.

Razrabota and low molecular weight mercaptans, including a preliminary alkalization of raw materials 1% aqueous solution of caustic soda for the selective extraction of extraction of the contained hydrogen sulfide and naphthenic acids, separation and further processing the partially purified material by oxygen and catalyst complex, representing 10-20% aqueous sodium hydroxide solution and 0.005% phthalocyaninato of catalyst YWCAS at 50-60oC and a pressure of about 1.2 MPa for the catalytic oxidation of light mercaptans to di - sulphide, separating the purified raw materials from the catalyst complex sedimentation and return on the last stage of the oxidative purification of raw materials from mercaptans (W. "Chemistry and technology of fuels and oils", 1996, 6, S. 11-12).

This process provides a relatively high degree of purification of raw materials from hydrogen sulfide, light mercaptans and getting deodorized oil.

The disadvantages of this process are its multi-stage, the scarcity and high cost of used phthalocyaninato of catalyst YWCAS and high consumption of caustic soda for cleaning raw materials from hydrogen sulfide and naphthenic acids, especially when cleaning the raw materials with high content of hydrogen sulfide, as well as education mean the IU, this process cannot be practically used for cleaning heavy sour crude oils due to the formation of persistent trudnorazreshimym emulsions of oil used with solutions of alkali and catalyst complex.

Closest to the proposed invention is a method of purification of oil and gas condensate from hydrogen sulfide and light mercaptans by air oxidation, is taken as 0.1 to 0.15 nm3air 1 mol of hydrogen sulfide and mercaptans FROM1-C3when 10-65oWith the pressure of 0.2-1.5 MPa and for 15-180 min in the presence as catalyst of monoethanolamine, taken in an amount of 0.01-0.1 wt.%. At the same time to accelerate the reaction of sweetening in oil or condensate impose additional elemental sulfur in a quantity of 0.05-0.2 wt.%. In addition, the process is carried out in the presence of phthalocyaninato catalyst, for example of desulfosarcina or dichlorodimethylsilane cobalt, taken in an amount of 0.05-1.0 g per 1 ton of oil or gas (U.S. Pat. RF 2114896, C 10 G 27/04, 1998).

This method provides a relatively high degree of purification of raw materials from hydrogen sulfide.

However, the disadvantage of this method is insufficient vysoko of monoethanolamine in the sweetening reaction. In addition, the preferred variant of the process in this way provides for the use as catalyst for the oxidation of scarce and expensive cobalt phthalocyanine, which leads to the appreciation of the cleaning process.

The objective of the invention is to increase the degree of purification of raw materials from mercaptans, as well as expanding the range of available and active catalysts for the oxidative purification of oil, gas condensate from hydrogen sulfide and mercaptans.

According to the invention the mentioned technical result is achieved by the described method for purification of oil, gas condensate from hydrogen sulfide and mercaptans by air oxidation at a temperature of 10-65oC and a pressure not less than 0.2 MPa in the presence of amino compounds as a catalyst, in which the latter make use of secondary or tertiary alkylamine, or tertiary alkanolamine, or mixtures thereof in an amount of 0.01-0.2 wt.% in the calculation of the original raw materials. At the same time as secondary and tertiary alkylamine is mainly used di - and trialkylamines1-C4and as tertiary alkanolamine - triethanolamine, methyldiethanolamine or mixtures thereof. In addition, when cleaning syringes pre-enter elemental sulfur in a quantity defined by the formula:

< / BR>
where So- the amount of added elemental sulfur, wt.%;

SRand SH- the content of mercaptan and hydrogen sulfide sulfur in the feedstock, respectively, wt.%;

1,7 - stoichiometric reaction coefficient sweetening materials.

The calculated amount of elemental sulfur is mainly injected into the feedstock is dissolved in the form of a solution in oil, condensate and/or in the applicable trialkylamine, trialkanolamines.

In addition, to accelerate the oxidation of hydrogen sulfide in the raw material with high content of hydrogen sulfide in addition enter the complex with ferric disodium salt of ethylenediaminetetraacetic acid or a complex of divalent cobalt with polyphosphate, preferably pyrophosphate rate of 0.05-3.0 g of the complex in 1 t of oil or condensate. While these complexes are preferably injected into the feedstock in the form of aqueous or aqueous-alkaline solution with a pH of not more than 10. Moreover, in the latter case, as the alkaline agent is an aqueous-alkaline solution of the complex mainly use water-aminosilane, preferably di-, triethanolamine, matildiche 1 mol of hydrogen sulfide and mercaptan sulfur, and the process is performed at a pressure of 0.3 to 3 MPa.

Distinctive features of the proposed method are the use of secondary and/or tertiary alkylamines followed and tertiary alkanolamines, mainly of the above di-, trialkylamines and triethanolamine, as catalysts for oxidation of hydrogen sulfide, mercaptans oxygen and sulfur in the environment of oil and gas condensate, as well as a preliminary introduction to the raw materials of elemental sulfur found in optimal quantities, determined by the above-mentioned experimentally established formula that takes into account the ratio of mercaptan and hydrogen sulfide sulfur in the feedstock, the stoichiometry flowing oxidation reactions and the resulting products of their oxidation by air oxygen and elemental sulfur. An additional distinguishing feature is the use of more accessible and affordable complexes of iron or cobalt instead of scarce phtalocyanines catalysts.

These distinctive features of the proposed technical solutions determine its novelty and inventive step in comparison with the prior art in this field, because they are not described in literature and help to improve the degree of purification of setlocal application process scarce, expensive phthalocyaninato catalyst and thereby reduce the cost of the cleanup process, as well as to expand the range of the used catalysts.

The need and feasibility of use as the amino compounds namely secondary, tertiary alkylamine or tertiary alkanolamine due to their much higher catalytic activity at the same time in the oxidation reaction of hydrogen sulfide with oxygen in the air and mercaptans elemental sulfur. Moreover, as shown in the results of the kinetic studies, the most high catalytic activity have tertiary alkylamines followed WITH1-C4and triethanolamine. They provide selective oxidation of hydrogen sulfide to elemental sulfur, which results in increased purity of raw materials from mercaptans under identical conditions compared to the use as catalyst of a primary amine, in particular monoethanolamine. This is because primary amines, including the IEA, already at normal temperature /20-50oWith/ actively react with elemental sulfur, including in the presence of hydrogen sulfide, with the formation of various polysulfides, and in the presence of water and thiosulfate IEA, CII with the IEA and thus not achieved satisfactory cleaning of raw materials from mercaptans. In addition, the IEA at ordinary temperatures is actively responding also contained in the feedstock acidic impurities: carbon dioxide, naphthenic acids, phenolic compounds, which also leads to the reduction of its catalytic activity in the oxidation reaction of hydrogen sulfide and mercaptans. Unlike the IEA tertiary and tertiary alkylamines followed alkanolamine at ordinary temperatures does not react with elemental sulfur, and only activate it, resulting in the oxidation of hydrogen sulfide and pre-entered sulfur is spent only on the oxidation of mercaptans contained with the formation of di-and partly trisulfide, and thus achieved a higher degree of purification of raw materials from mercaptans. Given this, and the availability, cost, toxicity and manufacturability, as a highly efficient catalyst for the process are encouraged to use trialkylamine2-C4, triethanolamine or mixtures thereof. We offer quantity /0,01-0,2%/ is optimal, since at concentrations less than 0.01% is required excessively long time oxidation /over 3 hours/ not achieved satisfactory cleaning of the raw material from which hydrogen sulfide, and an increase in the amount of more than 0.2% economically Neale the range from 0.03 to 0.15 wt.% depending on the content of hydrogen sulfide and mercaptans in the feedstock.

Prior to the introduction of the feedstock is dissolved sulfur is not required in cases where the content of mercaptan and hydrogen sulfide sulfur in the ratio 1:1 or less, as in the proposed method contains hydrogen sulfide is selectively oxidized to sulfur, adverse reactions of sulfur with the used catalyst in the temperature range 10-65oWith almost no flow and the resulting elemental sulfur sufficient to oxidize the contained volatile and the most toxic of mercaptans 1-C4. Preliminary introduction sulfur is required only in cases increased in comparison with the hydrogen sulfide content of mercaptan sulfur and a sufficient amount is calculated according to the formula above for each specific type of feedstock /see examples 4-7/. The introduction of sulfur in quantities exceeding the calculated optimum value, though, and leads to some increase in the speed and degree of purification of raw materials from mercaptans, but it is not economically feasible because of the unreasonably high consumption of sulfur and, more importantly, increase the total sulfur in the purified raw materials.

Additional introduction into the reaction mixture of the above complexes of iron or cobalt, as phthalocyaninate with high content of hydrogen sulfide and mercaptans, because in normal concentrations sufficiently high reaction rate of oxidation is achieved in the presence as catalyst only tertiary and secondary amines. With the introduction of less than 0.05 g/t above complex of iron or cobalt is not noticeable acceleration of the speed of the oxidation reaction, and the increase in the amount of more than 3 g/t is not economically feasible due to its unreasonably high flows. It should be stated that the above complexes of iron and cobalt at the same time accelerate the oxidation of the contained mercaptans to disulfides, which are confirmed by literature data (g. "Oil, gas and petrochemicals abroad", M., Nedra, 1988, 1, S. 108; kN. Shigeru UAE "Chemistry of organic sulfur compounds", M., Chemistry, 1975, S. 101 and others). It should also be noted that in the proposed method, in principle, can be used and phthalocyanines, cobalt and iron, however, as mentioned above, they are scarce and expensive products.

The proposed amount of air for oxidation /1.1 to 1.6 mol of oxygen per 1 mol of hydrogen sulfide and mercaptan sulfur/ associated with stoichiometry flowing oxidation reactions and is optimal with regard to loss of oxygen with the spent nuclear. Increasing the amount of oxygen taken more than 1.6 mol, as well as increasing process pressure above 3 MPa is not economically feasible due to increasing energozatrat to conduct the cleaning process.

The proposed method is tested in laboratory conditions and is illustrated by the following specific, but not limiting, examples.

Example 1. Into the reaction flask with a capacity of 250 ml is placed computational load diethylamine technical GOST 9875-88 and 100 ml of anhydrous sulphurous oil containing 0,021 wt.% hydrogen sulfide sulfur and to 0.022 wt.% mercaptan sulfur. The ratio of mercaptan and hydrogen sulfide sulfur in the original oil is approximately equal to 1: 1, so a preliminary introduction to the raw elemental sulfur is not required; concentration taken diethylamine is 0.05 wt.%. Then the reaction flask is rinsed technical oxygen from an oxygen cylinder that allows you to simulate the process of refining oil oxidation compressed air at a pressure of about 0.5 MPa, the flask is closed with an airtight stopper and intensively stirred at 40oC. After stirring for 1.5 h conduct a quantitative analysis of the purified oil content of hydrogen sulfide and mercaptans 100% and mercaptans - 41%.

Example 2. Cleaning sulfur oil containing 0,021 wt.% hydrogen sulfide sulfur and to 0.022 wt.% mercaptan sulfur, spend the same conditions of example 1, but using as the catalyst of triethylamine technical GOST 9966-88 in the amount of 0.11 wt.%. The degree of purification of oil from the hydrogen sulfide is 100% and mercaptans - 66%.

Example 3. Cleaning sulfur oil containing 0,021 wt.% hydrogen sulfide sulfur and to 0.022 wt. % mercaptan sulfur, spend the same conditions of example 1, but using as the catalyst triethanolamine technical on THE 6-02-916-85 in the amount of 0.2 wt.%. The degree of purification of oil from the hydrogen sulfide is 100% and mercaptans - 44%.

Example 4. Cleaning sulfur oil containing a 0.035 wt.% hydrogen sulfide sulfur and 0.11 wt.% mercaptan sulfur, carried out analogously to example 1 using as the catalyst of triethylamine in the amount of 0.15 wt.%. The ratio of mercaptan and hydrogen sulfide sulfur in the original oil is more than 1 /0,11:0,0353/ and therefore requires a preliminary introduction to the raw materials of elemental sulfur, the amount of which is calculated according to the formula above and is: So=/0,11-0,035/:1,7=0,04 wt.% per IP the Institute in the form of a 1.5% solution in the same oil in an amount of 3 ml After the introduction of the sulphur solution and the catalyst is triethylamine the reaction flask filled with oxygen, close sealed tube and intensively stirred at 40oC for 1.5 h, the Degree of purification of oil from the hydrogen sulfide is 100% and mercaptans - 56%.

Example 5. Cleaning sulfur oil containing 0.05 wt.% hydrogen sulfide and 0.44 wt.% mercaptan sulfur, carried out analogously to example 1 using as the catalyst of triethylamine in the amount of 0.11 wt.%. The ratio of mercaptan and hydrogen sulfide sulfur in the original oil is more than 1 /0,44: 0,05= 8,8/ and therefore requires a preliminary introduction to the original oil of elemental sulfur in the amount of: /0,44-0,05/:1,7=0,23 wt.% in the calculation of the original oil.

The estimated amount of sulfur injected into the feedstock in the form of a 1.5% solution in oil and applied triethylamine. In addition, given the high content of hydrogen sulfide and mercaptans, to accelerate the oxidation reactions in the original oil is further added an aqueous-alkaline solution of the complex with ferric disodium salt of ethylenediaminetetraacetic acid/Trilon B/ having a pH of 8.5 and the concentration of the iron complex 7 wt.% at the rate of 3.0 g/t of oil. Premastering of iron in water and adding water-soluble amine - triethanolamine to achieve a desired pH of 8.5. Then the reaction flask filled with oxygen and intensively stirred at 40oC for 1.5 h, the Degree of purification of oil from the hydrogen sulfide is 100% and from mercaptans to 54%.

Example 6. Purification of high-carbon oil containing 0.06 wt. % hydrogen sulfide and 0.18 wt.% mercaptan sulfur, carried out analogously to example 1 using as the catalyst of triethylamine in the amount of 0.15 wt.%. The ratio of mercaptan and hydrogen sulfide sulfur in the original oil is more than 1 and, therefore, requires a preliminary introduction of elemental sulfur in the amount of: /0,18-0,06/:1,7==0,07 wt.%.

The estimated amount of sulfur introduced into the original oil in the form of a 1.5% solution in petroleum and triethylamine. In addition, the oil is further added an aqueous solution of a complex of divalent cobalt with pyrophosphate at the rate of 0.5 g/t oil. Then the reaction flask filled with oxygen and intensively stirred at 60oC for 1 h, the Degree of purification of oil from the hydrogen sulfide is 100% and mercaptans - 58%.

The odor of hydrogen sulfide and light mercaptans in purified according to examples 1-6 raw materials out of line not obnarujivaet storage, transportation and processing.

Comparative experiment on cleaning sulfur oil containing 0,021 wt. % sulfur and hydrogen sulfide to 0.022 wt.% mercaptan sulfur, in the conditions of example 1 showed that when carrying out the known method of the prototype with the use as catalyst of monoethanolamine in the amount of 0.05 wt.% the degree of purification from hydrogen sulfide is 100% and mercaptans - 15%. The purified oil has a specific smell of light mercaptans.

Example 7. Purification of high-carbon oil containing 0.06 wt. % hydrogen sulfide and 0.18 wt.% mercaptan sulfur, carried out analogously to example 1 using as the catalyst of methyldiethanolamine in an amount of 0.1 wt.%. The ratio of mercaptan and hydrogen sulfide sulfur in the original oil more than 1 and, therefore, requires a preliminary introduction of elemental sulfur in the amount of: (0,18-0,06)/1,7=0,07 wt.%.

The estimated amount of sulfur introduced into the original oil in the form of a 1.5% solution in petroleum and methyldiethanolamine. In addition, the oil is further added an aqueous solution of the complex dvukhvalentnogo cobalt with pyrophosphate at a rate of 1 g/t of oil. Then the reaction flask filled with oxygen and mix the practical smell of hydrogen sulfide and light mercaptans in the purified oil is out of line is not detected, ie is achieved deodorization of sour crude oil and decrease its toxicity, corrosional for subsequent storage and transportation.

The data presented in examples 1-7 show that the purification of hydrogen sulfide - and mercaptoacetate hydrocarbons of the proposed method in comparison with the known leads to significantly improve the degree of purification from mercaptans /4166 and 15%, respectively,/ while maintaining the degree of purification from hydrogen sulfide at a high level. In addition, the process of the proposed method eliminates the use of scarce and expensive phthalocyaninato catalyst and thereby reduce the cost of the cleanup process, as well as to expand the range of the used catalysts. The proposed method, as known, can be used for cleaning heavy sour crude oils, forming with alkaline solutions traderstewie emulsion.

1. The purification method of crude oil, gas condensate from hydrogen sulfide and mercaptans by air oxidation at a temperature of 10-65oC and a pressure of not less than 0.2 MPa in the presence of amino compounds as catalyst, characterized in that as the last use of secondary or ASS="ptx2">

2. The method according to p. 1, characterized in that as the secondary and tertiary alkylamine mostly use di-, trialkylamine C1-C4and as tertiary alkanolamine - triethanolamine, methyldiethanolamine or mixtures thereof.

3. The method according to p. 1, characterized in that the refining of the raw material containing the mercaptan and hydrogen sulfide sulfur in the ratio of SR:SHmore than 1 in oil or condensate pre-enter the elemental sulfur in the amount determined by the formula

< / BR>
where So- the amount of added elemental sulfur, wt.%;

SRand SH- the content of mercaptan and hydrogen sulfide sulfur in the feedstock, respectively, wt.%;

1,7 - stoichiometric reaction coefficient sweetening materials.

4. The method according to any of paragraphs.1-3, characterized in that the process is carried out in the presence of a complex with ferric disodium salt of ethylenediaminetetraacetic acid or a complex of divalent cobalt with polyphosphate, taken in an amount of 0.05 to 3.0 g per 1 ton of oil or gas.

5. The method according to any of paragraphs.1-4, characterized in that the air oxidation is taken from the calculation of 1.1 to 1.6 mol of oxygen per 1 mol of hydrogen sulfide and Merck

 

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