CN101812317B - Stabilizing agent of H2S in liquid hydrocarbon - Google Patents
Stabilizing agent of H2S in liquid hydrocarbon Download PDFInfo
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- CN101812317B CN101812317B CN 201010156614 CN201010156614A CN101812317B CN 101812317 B CN101812317 B CN 101812317B CN 201010156614 CN201010156614 CN 201010156614 CN 201010156614 A CN201010156614 A CN 201010156614A CN 101812317 B CN101812317 B CN 101812317B
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- stablizer
- liquid hydrocarbon
- agent
- hydramine
- nitrogen oxygen
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a stabilizing agent of H2S in liquid hydrocarbon, which consists of the following components in percentage by weight: 5 to 50 percent of nitrogen-oxygen heterocyclic compound, 5 to 75 percent of alcohol amine and 5 to 50 percent of auxiliary agent. The stabilizing agent of the H2S in the liquid hydrocarbon not only is non-corrosive, non-emulsive and non-scaling, but also has the geed effects of quick and thorough reaction with the H2S in the liquid hydrocarbon, high utilization ratio and small used amount, and also has the advantages of direct filling into the liquid hydrocarbon containing the H2S by a metering pump, small process, small equipment investment and unnecessary recovery of agents.
Description
Technical field
The present invention relates to the petroleum and petrochemical industry field, particularly H in a kind of liquid hydrocarbon
2The stablizer of S.
Background technology
In oil production and the processing, the H in the liquid hydrocarbons such as wet oil, dewatered oil, processed oil, liquefied gas, lighter hydrocarbons
2S can etching apparatus, causes safety and environmental protection hidden danger after the leakage, should remove or stablizes.
H commonly used
2The S removal methods be in order to mineral alkali, organic bases, solvent or oxygenant be host remove that agent removes or stable.Wherein: mineral alkali, organic bases by with H
2S carries out neutralization reaction, reaches to remove or stable H
2The purpose of S, the most frequently used mineral alkali H
2The weak point that S removes agent be can with liquid hydrocarbon in the water mutual effect, cause the emulsification of fouling, the profit of equipment, to the corrosion of equipment; Organic bases H
2S removes agent, as: ZL200810197680.5, ZL200910019796.4 etc., its weak point is that speed of response is slow, consumption is big, cost is high; Solvent-extracted main purpose is the organosulfur that removes in the liquid hydrocarbon, also can remove H simultaneously
2S, as ZL200510020482.8 etc., its weak point is that solvent needs to reclaim, agent-oil ratio is big, solvent reclaimer is numerous and diverse etc.; And oxygenant H
2It mainly is the oxygenizement of using oxygenant that S removes agent, makes the H in the liquid hydrocarbon
2S becomes the comparatively stable S of character or SO
4 2-Reach and remove or stable H
2The purpose of S, as: ZL200710158373.1 etc., its weak point is the corrosion of equipment stronger.
The technology of the acid gas removal agent in the industrial gasses of being made up of hydramine, auxiliary agent and additive that recycle is a lot, but speed of response is slow in liquid hydrocarbon, consumption is big, cost is high, reclaim the medicament difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of not only non-scaling, not emulsification of burn into, add that dose is little, medicament does not need to reclaim, technology is simple and with hydrocarbon liquid phase in H
2The S speed of response is fast, consumption is little, react the H in the liquid hydrocarbon completely
2The agent of S efficient stable.
Technical scheme of the present invention is: H in a kind of liquid hydrocarbon
2The efficient stable agent of S, by weight percentage, the nitrogen oxygen helerocyclics by 5～50%, 5～75% hydramine, 5～50% auxiliary agent are formed, and it is characterized in that the chemical structural formula of the nitrogen oxygen helerocyclics that contains in the stablizer is:
Wherein: R
1For :-H ,-NH
2,-CH
3,-CH
2NH
2,-CH
2OH-CH
2CH
3,-CH
2CH
2NH
2,-CH
2CH
2OH
R
2, R
2', R
3, R
3' be :-H ,-CH
3,-CH
2CH
3,-CH
2OH
R
4, R
4', R
5, R
5' be :-H ,-CH
3,-Pr-n ,-Bu-n
R
6, R
6' be :-CH
2-,-CH
2CH
2-.
Above-mentioned structural formula is the nitrogen oxygen helerocyclics of (I), (II) and (III), be respectively to adopt hydramine and carbonyl compound to be respectively the feed ratio of 1:1,1:2 and 2:3 according to mol ratio, and under the condition of 30～95 ℃ of stirring heating, the 0.5～8h that refluxes, react colourless, the faint yellow or yellow liquid of producing; Structural formula adopts a kind of hydramine for the nitrogen oxygen helerocyclics of (I) and (II) when synthetic, and structural formula when be the nitrogen oxygen helerocyclics of (III) synthesize two kinds of hydramine of employing according to the pure amine mixt of the mol ratio of 1:1.The most frequently used carbonyl compound is formaldehyde, polyoxymethylene etc.
Above-mentioned hydramine is a kind of or mixture in single thanomin, Mono Methyl Ethanol Amine, dimethylethanolamine, diethanolamine, methyldiethanolamine, trolamine, the diisopropanolamine (DIPA).
Above-mentioned auxiliary agent is a kind of or mixture in tetramethylene sulfone, nylon acid methyl esters, nylon acid dimethyl ester, many ethylene glycol monomethyl ethers, many glycol dimethyl ethers, methyl-2-pyrrolidone, morpholine, formyl morpholine, the ethanoyl morpholine.
Can add additive in the above-mentioned stablizer, additive can be conventional defoamer or inhibiter, and addition is 0.05～0.5% of stablizer weight.
Softening water can be added in the above-mentioned stablizer, H in the liquid hydrocarbon can be improved
2Efficient stable agent and the H of S
2The speed of response of S and utilization ratio, addition are 5～150% of stablizer weight.
The usage of above-mentioned stablizer is directly to inject 0.01～1% of liquid hydrocarbon weight in liquid hydrocarbon with volume pump, does not reclaim the medicament of injection.
In the industrial gasses of being formed by hydramine, auxiliary agent and additive that recycle, in the acid gas removal agent, add the nitrogen oxygen helerocyclics of a kind of ad hoc structure disclosed by the invention, be used as H in the liquid hydrocarbon
2The agent of S efficient stable is gordian technique of the present invention.
The invention has the beneficial effects as follows: the H in the liquid hydrocarbon of the present invention
2The agent of S efficient stable, mixing with liquid hydrocarbon does not only have not emulsification of burn into, non-scaling, and have with liquid hydrocarbon in H
2The good result that the S reaction is fast, reaction is thorough, utilization ratio is high, consumption is few.With volume pump directly to containing H
2Annotate in the liquid hydrocarbon of S, technology is simple, facility investment is little, does not need to reclaim medicament.
Embodiment
Further set forth the present invention below in conjunction with embodiment.
H of the present invention
2Moisture H is used in the agent of S efficient stable in the liquid hydrocarbon that can add less water such as crude oil, lighter hydrocarbons etc.
2The agent of S efficient stable, speed of response can be faster, consumption is littler, utilization ratio is higher; In the processed oil that can not add water, liquefied gas etc., use anhydrous H
2The efficient stable agent of S also has good effect.
Embodiment 1:
Selecting structure for use is the R of (I)
1For-CH
3, R
2, R
3, R
4, R
5Be the nitrogen oxygen helerocyclics 15% of-H, and the ratio of methyldiethanolamine 40%, many glycol dimethyl ethers 25%, nylon acid dimethyl ester 20% is mixed with anhydrous H
2The agent of S efficient stable; Add anhydrous H
2The softening water of S efficient stable agent gross weight 20% is mixed with moisture H
2The agent of S efficient stable.
Select moisture H for use
2The agent of S efficient stable, the ZG10 well is tested in the oil field, Tarim Basin, this well day producing natural gas 10 * 10
4m
3/ d produces moisture 12% crude oil 65t/d daily, the H that volatilizes in the crude oil after the gas-liquid separation
2S concentration is 8100ppm, with the moisture H that adds former weight of oil 0.15% in the crude oil of volume pump after the gas-liquid separation
2The agent of S efficient stable is 75 seconds in the following reaction times of normal condition, the H that volatilizes in the crude oil of handling after testing
2S is 3ppm, is far smaller than the control index of 20ppm.
Select anhydrous H for use
2The agent of S efficient stable is tested in the liquefied gas of the cracking process production of North China Oilfield petro-chemical corporation, and this liquefied gas contains H
2The concentration of S is 2184ppm, contains mercaptan 132ppm, adds the anhydrous H of liquefied gas weight 0.10% in the liquefied gas with volume pump
2The agent of S efficient stable, the reaction times is about 360 seconds, the H in the liquefied gas of handling after testing
2S is 13ppm, and mercaptan is 82ppm, and clearance is respectively 99.4% and 37.9%.
Embodiment 2:
Selecting structure for use is the R of (I)
1For-CH
2CH
2NH
2, R
2, R
3, R
4, R
5Be the nitrogen oxygen helerocyclics 12% of-H, and the single thanomin 48% of dimethyl, many ethylene glycol monomethyl ethers 25%, nylon acid dimethyl ester 15% ratio are mixed with anhydrous H
2The agent of S efficient stable; Add anhydrous H
2The softening water of S efficient stable agent gross weight 50% is mixed with moisture H
2The agent of S efficient stable.
Select moisture H for use
2The agent of S efficient stable is tested at oil field, Tarim Basin ZG10 well equally, with the moisture H that adds former weight of oil 0.20% in the crude oil of volume pump after the gas-liquid separation
2The agent of S efficient stable, the H that volatilizes in the crude oil of handling after testing
2S is 9ppm.
Select anhydrous H for use
2The agent of S efficient stable is tested in the liquefied gas of the cracking process production of North China Oilfield petro-chemical corporation equally, adds the anhydrous H of liquefied gas weight 0.15% in the liquefied gas with volume pump
2The agent of S efficient stable, the H in the liquefied gas of handling after testing
2S is 16ppm, and mercaptan is 32ppm, and clearance is respectively 99.3% and 75.8%.
Embodiment 3:
Selecting structure for use is the R of (II)
3For-CH
2CH
3, R
4, R
4', R
5, R
5' be-the nitrogen oxygen helerocyclics 25% of H, and diethanolamine 45%, many ethylene glycol monomethyl ethers 20%, morpholine 10% ratio are mixed with anhydrous H
2The agent of S efficient stable; Add anhydrous H
2The softening water of S efficient stable agent gross weight 80% is mixed with moisture H
2The agent of S efficient stable.
Select moisture H for use
2The agent of S efficient stable is tested at oil field, Tarim Basin ZG10 well equally, adds the moisture H of former weight of oil 0.25% in the crude oil with volume pump
2The S stablizer, the H that volatilizes in the crude oil of handling after testing
2S is 12ppm.
Select anhydrous H for use
2The agent of S efficient stable is tested in the liquefied gas of the cracking process production of North China Oilfield petro-chemical corporation equally, adds the anhydrous H of liquefied gas weight 0.20% in the liquefied gas with volume pump
2The agent of S efficient stable, the H in the liquefied gas of handling after testing
2S is 27ppm, and mercaptan is 39ppm, and clearance is respectively 98.8% and 70.5%.
Embodiment 4:
Selecting structure for use is the R of (III)
6For-CH
2CH
3-, R
6' be-CH
2-, R
2, R
2', R
3, R
3', R
4, R
4', R
5, R
5' be-the nitrogen oxygen helerocyclics 30% of H, and mixture 40%, formyl morpholine and the mixture 15% of ethanoyl morpholine (1:1), many ethylene glycol monomethyl ethers 15% ratio of single thanomin and methyldiethanolamine (1:1) are mixed with anhydrous H
2The agent of S efficient stable; Add anhydrous H
2The softening water of S efficient stable agent gross weight 110% is mixed with moisture H
2The agent of S efficient stable.
Select moisture H for use
2The agent of S efficient stable is tested at oil field, Tarim Basin ZG10 well equally, adds the moisture H of former weight of oil 0.30% in the crude oil with volume pump
2The S stablizer, the H that volatilizes in the crude oil of handling after testing
2S is 17ppm.
Select anhydrous H for use
2The agent of S efficient stable is tested in the liquefied gas of the cracking process production of North China Oilfield petro-chemical corporation equally, adds the anhydrous H of liquefied gas weight 0.25% in the liquefied gas with volume pump
2The agent of S efficient stable, the H in the liquefied gas of handling after testing
2S is 6ppm, and mercaptan is 22ppm, and clearance is respectively 99.9% and 83.3%.
In an embodiment of the present invention, in order to improve H
2The over-all properties of S efficient stable agent has all been added additives such as conventional defoamer, inhibiter, the consumption of additive be total amount 0.05～0.5% but do not count in the total amount; Not adding additive can not influence yet and remove or stable H
2The effect of S.
Above embodiment proves: H of the present invention
2The agent of S efficient stable not only can be stablized the H in the liquid hydrocarbon rapidly under conventional working condition
2S, and certain mercaptan removal effect is arranged.Detect through routine, no matter in liquid hydrocarbons such as water-free oil, wet oil, processed oil, liquefied gas, lighter hydrocarbons, do not have the problem that causes emulsification, fouling and corrosion, and equipment is simple, consumption is few, reaction conditions require low, be swift in response and thoroughly, and have medicament not need to reclaim, technology is simple, investment is little advantage.
Claims (6)
1. H in the liquid hydrocarbon
2The stablizer of S is characterized in that: stablizer by weight percentage, the nitrogen oxygen helerocyclics by 5～50%, 5～75% hydramine and 5～50% auxiliary agent are formed;
The chemical structural formula of described nitrogen oxygen helerocyclics is:
Wherein:
R
1For :-H ,-NH
2,-CH
3,-CH
2NH
2,-CH
2OH ,-CH
2CH
3,-CH
2CH
2NH
2,-CH
2CH
2OH;
R
2, R
2 ,, R
3, R
3 ,For :-H ,-CH
3,-CH
2OH ,-CH
2CH
3,-CH
2CH
2OH;
R
4, R
4 ,, R
5, R
5 ,For :-H ,-CH
3,-Pr-n ,-Bu-n;
R
6, R
6 ,For :-CH
2-,-CH
2CH
2-;
Described auxiliary agent is a kind of or mixture in tetramethylene sulfone, nylon acid methyl esters, nylon acid dimethyl ester, many ethylene glycol monomethyl ethers, many glycol dimethyl ethers, methyl-2-pyrrolidone, morpholine, formyl morpholine, the ethanoyl morpholine.
2. H in the liquid hydrocarbon according to claim 1
2The stablizer of S is characterized in that: the hydramine in the described stablizer is a kind of or mixture in single thanomin, Mono Methyl Ethanol Amine, dimethylethanolamine, diethanolamine, methyldiethanolamine, trolamine, the diisopropanolamine (DIPA).
3. H in the liquid hydrocarbon according to claim 1
2The stablizer of S is characterized in that: in the stablizer or add softening water, addition is 5～150% of stablizer weight.
4. H in the liquid hydrocarbon according to claim 1
2The stablizer of S is characterized in that: in the stablizer or add additive, addition is 0.05～0.5% of stablizer weight; Described additive is conventional defoamer or inhibiter.
5. H in the described liquid hydrocarbon of claim 1
2The preparation method of the stablizer of S, it is characterized in that: described structural formula is the nitrogen oxygen helerocyclics of (I), (II) and (III), adopting hydramine and carbonyl compound respectively is the feed ratio of 1:1,1:2 and 2:3 according to mol ratio, and under the condition of stirring, 30～95 ℃ of heating, the 0.5～8h that refluxes, react colourless, the faint yellow or yellow liquid of producing; Structural formula adopts a kind of hydramine for the nitrogen oxygen helerocyclics of (I) and (II) when synthetic, and structural formula when be the nitrogen oxygen helerocyclics of (III) synthesize two kinds of hydramine of employing according to the pure amine mixt of the mol ratio of 1:1.
6. H in the described liquid hydrocarbon of claim 1
2The application of the stablizer of S is characterized in that: use is directly to inject 0.01～1% of liquid hydrocarbon weight in liquid hydrocarbon with volume pump, does not reclaim the medicament of injection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010156614 CN101812317B (en) | 2010-04-27 | 2010-04-27 | Stabilizing agent of H2S in liquid hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010156614 CN101812317B (en) | 2010-04-27 | 2010-04-27 | Stabilizing agent of H2S in liquid hydrocarbon |
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| Publication Number | Publication Date |
|---|---|
| CN101812317A CN101812317A (en) | 2010-08-25 |
| CN101812317B true CN101812317B (en) | 2013-07-10 |
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| CN 201010156614 Expired - Fee Related CN101812317B (en) | 2010-04-27 | 2010-04-27 | Stabilizing agent of H2S in liquid hydrocarbon |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816585B (en) * | 2012-08-16 | 2014-05-28 | 西安建筑科技大学 | Oil-soluble desulfurizer, and preparation and application thereof |
| CN104451699B (en) * | 2014-11-20 | 2016-08-24 | 中国石油天然气集团公司 | A kind of H2s-HCl-H2o system high-temperature corrosion inhibitor and preparation method thereof |
| CN105056710B (en) * | 2015-08-21 | 2017-05-24 | 胜利油田胜利化工有限责任公司 | Liquid absorbent for removing hydrogen sulfide in oil gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107236A (en) * | 1985-10-28 | 1987-10-07 | 陶氏化学公司 | The sweetening of hydrocarbons process |
| CN1169334A (en) * | 1996-06-20 | 1998-01-07 | 中国石化辽阳石油化纤公司 | Acidic gas absorbent and preparation method thereof |
| CN1465718A (en) * | 2002-06-21 | 2004-01-07 | 四川大学 | Chrome free or less chrome main tanning agent for leather and preparation process thereof |
-
2010
- 2010-04-27 CN CN 201010156614 patent/CN101812317B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107236A (en) * | 1985-10-28 | 1987-10-07 | 陶氏化学公司 | The sweetening of hydrocarbons process |
| CN1169334A (en) * | 1996-06-20 | 1998-01-07 | 中国石化辽阳石油化纤公司 | Acidic gas absorbent and preparation method thereof |
| CN1465718A (en) * | 2002-06-21 | 2004-01-07 | 四川大学 | Chrome free or less chrome main tanning agent for leather and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| "有机醇胺溶液吸收选择性脱除H2S";陆建刚等;《天然气化工》;20071231;第32卷(第6期);第63-69页 * |
| 陆建刚等."有机醇胺溶液吸收选择性脱除H2S".《天然气化工》.2007,第32卷(第6期),第63-69页. |
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|---|---|
| CN101812317A (en) | 2010-08-25 |
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