CN102816584A - Water-soluble desulfurization agent, preparation and application thereof - Google Patents
Water-soluble desulfurization agent, preparation and application thereof Download PDFInfo
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- CN102816584A CN102816584A CN2012102923093A CN201210292309A CN102816584A CN 102816584 A CN102816584 A CN 102816584A CN 2012102923093 A CN2012102923093 A CN 2012102923093A CN 201210292309 A CN201210292309 A CN 201210292309A CN 102816584 A CN102816584 A CN 102816584A
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Abstract
A water-soluble desulfurization agent uses water as a solvent, and comprises solutes of 16-27 wt% of methyldiethanolamine (MDEA), 2.8-4.2 wt% of diethanol amine (DEA), 3.3-4.8 wt% of sulfolane, and 60-68 wt% of sodium nitrite. The invention also provides a preparation method of the water-soluble desulfurization agent. The obtained water-soluble desulfurization agent can be used to reduce hydrogen sulfide gas in crude oil, not only has excellent instant desulfurization performance, but also can reduce the quantity of sulfate reducing bacteria in crude oil and hydrogen sulfide gas produced by metabolism of the bacteria sulfate reducing bacteria, so as to enhance sustainable capability of the desulfurization agent. According to calculation, the desulfurization agent provided by the invention has sulfur capacity of 80 mg / L and addition amount of 40ml, can reduce 1200 ppm to 10 ppm in 30 minutes, and reaches requirements of the Occupational Exposure Limit for Hazardous Agents in the Workplace.
Description
Technical field
The invention belongs to the oil desulfurization technical field, relate to the processing of high-hydrogen sulfide crude oil, be specifically related to a kind of water-soluble sweetening agent and preparation and application.
Background technology
H2S is a kind of hypertoxic gas, and is serious to human harm.With regard to petroleum industry, the distribution of H2S gas is very extensive, operating worker is existed potential safety hazards such as potential life injury.Corrosion oil transportation official website and downstream refining device, and polluted surrounding environment to a certain extent, bring certain potential safety hazard for simultaneously oil field employee and resident.Related Experimental Study shows that the hydrogen sulfide major part is a sulphate reducing bacteria metabolism gained in oil well and the gathering system.At present domesticly mainly contain dry desulfurization and wet desulphurization about the oil field sweetening agent.Though these sweetening agents can be reduced to 10mg/m with concentration of hydrogen sulfide in the short period of time
3, reach relevant criterion, but lasting poor.Therefore, research and develop a kind of simple to operation, effect is good, persistence is long water-soluble sweetening agent, oilfield transportation system hydrogen sulfide is suppressed, realize that oil field environment protection and energy-saving and emission-reduction have great importance.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art; The object of the present invention is to provide a kind of water-soluble sweetening agent and preparation and application; This sweetening agent not only can absorb the hydrogen sulfide in the crude oil through the rapid effective chemical of quaternary ammonium salt, also suppresses the hydrogen sulfide that the sulphate reducing bacteria metabolism produces through the environmental factors that changes in the crude oil.This sweetening agent use is simple, respond well, broad spectrum is strong.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of water-soluble sweetening agent is a solvent with water, and solute is:
Methyldiethanolamine (MDEA), massfraction 16%-27%;
Diethylolamine (DEA), massfraction 2.8%-4.2%;
Tetramethylene sulfone, massfraction 3.3%-4.8%;
Sodium Nitrite, massfraction 60%-68%.
Further, solute is:
Methyldiethanolamine (MDEA), massfraction 27%;
Diethylolamine (DEA), massfraction 2.8%;
Tetramethylene sulfone, massfraction 3.3%;
Sodium Nitrite, massfraction 66.4%.
The present invention provides the method for preparing said water-soluble sweetening agent simultaneously, comprises the steps:
Step 1 is got the 400-500g Sodium Nitrite and is dissolved in the 1000ml water and prepares sodium nitrite solution;
Step 2 is dripped the 33-50ml diethylolamine to the 200-330ml methyldiethanolamine, is positioned over 4 ℃ of refrigerator and cooled after titration finishes but 24 hours;
Step 3 with 50 ℃ of heating in water bath 30min of 33-100ml tetramethylene sulfone, adds in the mixing solutions of cooling back then;
Step 4; Methyldiethanolamine, tetramethylene sulfone and diethanolamine solution are positioned in the shaking table; Take out after shaking 30min,, allocate concentration with zero(ppm) water in the process according to the sodium nitrite solution of the step 1 preparation of Sodium Nitrite mass concentration adding respective amount in the final sweetening agent;
Step 5, the mixed solution that leaves standstill after 72 hours is made sweetening agent.
Further, at the uniform velocity splash in the methyldiethanolamine in the said diethylolamine 30min, at the uniform velocity splash in the mixing solutions in the tetramethylene sulfone 30min.
Said water-soluble sweetening agent can be used for reducing the crude oil hydrogen sulfide.
Compared with prior art; Sweetening agent of the present invention not only has good moment desulfurization performance; Can also reduce the quantity of sulphate reducing bacteria in the crude oil, reduce the hydrogen sulfide that produces by the sulphate reducing bacteria metabolism, thereby reach the purpose of the continuous capability that improves sweetening agent.Through measuring and calculating, the Sulfur capacity of this sweetening agent is 80mg/L, and addition is 40ml, can 1200ppm be reduced to 10ppm in 30 minutes, reaches the requirement of country's " harmful occupational factor contact place, working space limit value ".
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment one
A kind of water-soluble sweetening agent is a solvent with water, and solute is: methyldiethanolamine (MDEA), massfraction 27%; Diethylolamine (DEA), massfraction 2.8%; Tetramethylene sulfone, massfraction 3.3%; Sodium Nitrite, massfraction 66.4%.
Its preparation method comprises the steps:
Step 1, the preparation sodium nitrite solution.Get 400g Sodium Nitrite particle in beaker, add zero(ppm) water, in the heating in water bath pot, behind 30-40 ℃ of thermostatically heating 30min of maintenance temperature, add stirring rotator and dissolve fully until Sodium Nitrite to 1000ml.
Step 2 is got in 330mlMDEA to the 1.5L beaker, under 30 ℃, gets 33mlDEA in the 50ml drop-burette in the placement shaking table, and 30min at the uniform velocity drips DEA to MDEA.After finishing, titration was positioned over 4 ℃ of refrigerator and cooled but 24 hours.
Step 3 is got the 50ml beaker, adds the 40ml tetramethylene sulfone, and behind 50 ℃ of heating in water bath 30min, gets the 33ml tetramethylene sulfone in drop-burette, drips to the MDEA and the DEA mixing solutions that cool off after 24 hours, keeps 30min completion titration.
Step 4 is placed MDEA, tetramethylene sulfone and DEA solution in the shaking table, takes out after shaking 30min.Pour the sodium nitrite solution of step 1 preparation in 1000ml graduated cylinder 600ml, and this 600ml sodium nitrite solution is poured in MDEA, tetramethylene sulfone and the DEA mixing solutions, add zero(ppm) water and to 1000ml, use stirring rotator to stir.
Step 5, the mixed solution that leaves standstill after 72 hours is made sweetening agent.
Embodiment two
A kind of water-soluble sweetening agent is a solvent with water, and solute is: methyldiethanolamine (MDEA), massfraction 16%; Diethylolamine (DEA), massfraction 4.19%; Tetramethylene sulfone, massfraction 4.8%; Sodium Nitrite, massfraction 75%.
Its preparation method comprises the steps:
Step 1, the preparation sodium nitrite solution.Get 400g Sodium Nitrite particle in beaker, add zero(ppm) water, in the heating in water bath pot, behind 30-40 ℃ of thermostatically heating 30min of maintenance temperature, add stirring rotator and dissolve fully until Sodium Nitrite to 1000ml.
Step 2 is got in 200mlMDEA to the 1.5L beaker, under 30 ℃, gets 50mlDEA in the 50ml drop-burette in the placement shaking table, and 10min at the uniform velocity drips DEA to MDEA.After finishing, titration was positioned over 4 ℃ of refrigerator and cooled but 24 hours.
Step 3 is got the 100ml beaker, adds the 60ml tetramethylene sulfone, and behind 50 ℃ of heating in water bath 30min, gets the 50ml tetramethylene sulfone in drop-burette, drips to the MDEA and the DEA mixing solutions that cool off after 24 hours, keeps 30min completion titration.
Step 4 is placed MDEA, tetramethylene sulfone and DEA solution in the shaking table, takes out after shaking 30min.Pour the sodium nitrite solution of step 1 preparation in 1000ml graduated cylinder 700ml, and this 700ml sodium nitrite solution is poured in MDEA, tetramethylene sulfone and the DEA mixing solutions, add zero(ppm) water and to 1000ml, use stirring rotator to stir.
Step 5, the mixed solution that leaves standstill after 72 hours is made sweetening agent.
Embodiment three
A kind of water-soluble sweetening agent is a solvent with water, and solute is: methyldiethanolamine (MDEA), massfraction 20%; Diethylolamine (DEA), massfraction 3.3%; Tetramethylene sulfone, massfraction 3.8%; Sodium Nitrite, massfraction 68%.
Its preparation method comprises the steps:
Step 1, the preparation sodium nitrite solution.Get 500g Sodium Nitrite particle in beaker, add zero(ppm) water, in the heating in water bath pot, behind 30-40 ℃ of thermostatically heating 30min of maintenance temperature, add stirring rotator and dissolve fully until Sodium Nitrite to 1000ml.
Step 2 is got in 250mlMDEA to the 1.5L beaker, under 30 ℃, gets 40mlDEA in the 50ml drop-burette in the placement shaking table, and 10min at the uniform velocity drips DEA to MDEA.After finishing, titration was positioned over 4 ℃ of refrigerator and cooled but 24 hours.
Step 3 is got the 50ml beaker, adds the 40ml tetramethylene sulfone, and behind 50 ℃ of heating in water bath 30min, gets the 40ml tetramethylene sulfone in drop-burette, drips to the MDEA and the DEA mixing solutions that cool off after 24 hours, keeps 30min completion titration.
Step 4 is placed MDEA, tetramethylene sulfone and DEA solution in the shaking table, takes out after shaking 30min.Pour the sodium nitrite solution of step 1 preparation in 1000ml graduated cylinder 700ml, and this 700ml sodium nitrite solution is poured in MDEA, tetramethylene sulfone and the DEA mixing solutions, add zero(ppm) water and to 1000ml, use stirring rotator to stir.
Step 5, the mixed solution that leaves standstill after 72 hours is made sweetening agent.
Through measuring; Above-mentioned four case are added in the crude oil gathering system by 80ppm; It is as shown in table 1 to leave standstill 30min gained concentration of hydrogen sulfide, can find out that concentration of hydrogen sulfide is reduced to 8ppm from 2000ppm, reaches " industrial site occupational protection standard " (GBZ2-2002) related request.
Contrast before and after table 1 high-concentration hydrogen sulfide gathering system is handled
Claims (6)
1. a water-soluble sweetening agent is a solvent with water, and solute is:
Methyldiethanolamine (MDEA), mass concentration 16%-27%;
Diethylolamine (DEA), mass concentration 2.8%-4.2%;
Tetramethylene sulfone, mass concentration 3.3%-4.8%;
Sodium Nitrite, mass concentration 60%-68%.
2. according to the said water-soluble sweetening agent of claim 1, it is characterized in that solute is:
Methyldiethanolamine (MDEA), mass concentration 27%;
Diethylolamine (DEA), mass concentration 2.8%;
Tetramethylene sulfone, mass concentration 3.3%;
Sodium Nitrite, mass concentration 66.4%.
3. prepare the method for the said water-soluble sweetening agent of claim 1, it is characterized in that, comprise the steps:
Step 1 is got the 400-500g Sodium Nitrite and is dissolved in the 1000ml water and prepares sodium nitrite solution;
Step 2 is dripped the 33-50ml diethylolamine to the 200-330ml methyldiethanolamine, is positioned over 4 ℃ of refrigerator and cooled after titration finishes but 24 hours;
Step 3 with 50 ℃ of heating in water bath 30min of 33-100ml tetramethylene sulfone, adds in the mixing solutions of cooling back then;
Step 4; Methyldiethanolamine, tetramethylene sulfone and diethanolamine solution are positioned in the shaking table; Take out after shaking 30min,, allocate concentration with zero(ppm) water in the process according to the sodium nitrite solution of the step 1 preparation of Sodium Nitrite mass concentration adding respective amount in the final sweetening agent;
Step 5, the mixed solution that leaves standstill after 72 hours is made sweetening agent.
4. according to the said water-soluble sweetening agent preparation method of claim 3, it is characterized in that, at the uniform velocity splash in the methyldiethanolamine in the said diethylolamine 30min.
5. according to the said water-soluble sweetening agent preparation method of claim 3, it is characterized in that, at the uniform velocity splash in the mixing solutions in the said tetramethylene sulfone 30min.
6. be used for reducing the purposes of crude oil hydrogen sulfide according to claim 1 or 2 said water-soluble sweetening agents.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045291A (en) * | 2013-01-15 | 2013-04-17 | 西安嘉宏石化科技有限公司 | Sulfide removing agent and sulfur removing method thereof |
| CN104212480A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Hydrogen sulfide gas desulfurizer for oil well workover treatment process |
| CN104263404A (en) * | 2014-10-22 | 2015-01-07 | 天津亿利科能源科技发展股份有限公司 | Water-soluble crude oil desulfurizing agent and preparation method thereof |
| CN104629792A (en) * | 2015-02-04 | 2015-05-20 | 浙江海洋学院 | Method for removing nitride from heavy oil |
| CN105797783A (en) * | 2016-04-06 | 2016-07-27 | 山东成泰化工有限公司 | Low-temperature crude oil catalyst and preparation method thereof |
| CN105833711A (en) * | 2016-05-20 | 2016-08-10 | 张锐 | Ecological environment-friendly desulfurizer and preparation method thereof |
| CN114455550A (en) * | 2022-01-20 | 2022-05-10 | 湖北索立德新能源科技有限责任公司 | Preparation method of lithium sulfide |
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| CN100518892C (en) * | 2007-06-07 | 2009-07-29 | 华东理工大学 | Method and device for removing hydrogen sulphide from mixture gas containing low-concentration hydrogen sulphide |
| CN102153997A (en) * | 2011-03-07 | 2011-08-17 | 天津亿利科能源科技发展股份有限公司 | Hydrogen sulfide treating agent for oil fields and method for treating hydrogen sulfide |
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| CN1887406A (en) * | 2005-06-27 | 2007-01-03 | 成都华西化工研究所 | Solvent for eliminating H2S from gas mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045291A (en) * | 2013-01-15 | 2013-04-17 | 西安嘉宏石化科技有限公司 | Sulfide removing agent and sulfur removing method thereof |
| CN103045291B (en) * | 2013-01-15 | 2014-11-05 | 西安嘉宏石化科技有限公司 | Sulfide removing agent and sulfur removing method thereof |
| CN104212480A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Hydrogen sulfide gas desulfurizer for oil well workover treatment process |
| CN104212480B (en) * | 2013-06-05 | 2016-02-10 | 中国石油天然气股份有限公司 | Hydrogen sulfide sweetening agent in a kind of workover rig service to oil well process |
| CN104263404A (en) * | 2014-10-22 | 2015-01-07 | 天津亿利科能源科技发展股份有限公司 | Water-soluble crude oil desulfurizing agent and preparation method thereof |
| CN104629792A (en) * | 2015-02-04 | 2015-05-20 | 浙江海洋学院 | Method for removing nitride from heavy oil |
| CN105797783A (en) * | 2016-04-06 | 2016-07-27 | 山东成泰化工有限公司 | Low-temperature crude oil catalyst and preparation method thereof |
| CN105833711A (en) * | 2016-05-20 | 2016-08-10 | 张锐 | Ecological environment-friendly desulfurizer and preparation method thereof |
| CN114455550A (en) * | 2022-01-20 | 2022-05-10 | 湖北索立德新能源科技有限责任公司 | Preparation method of lithium sulfide |
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Application publication date: 20121212 |