CN102719268A - Method for converting mercaptan in crude oil - Google Patents
Method for converting mercaptan in crude oil Download PDFInfo
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- CN102719268A CN102719268A CN2012102230117A CN201210223011A CN102719268A CN 102719268 A CN102719268 A CN 102719268A CN 2012102230117 A CN2012102230117 A CN 2012102230117A CN 201210223011 A CN201210223011 A CN 201210223011A CN 102719268 A CN102719268 A CN 102719268A
- Authority
- CN
- China
- Prior art keywords
- crude oil
- mercaptan
- alkyl
- sulfocompound
- aldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000010779 crude oil Substances 0.000 title claims abstract description 52
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 11
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000009466 transformation Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 238000011033 desalting Methods 0.000 claims description 2
- 238000004148 unit process Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract description 3
- 238000005504 petroleum refining Methods 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 3
- 230000007547 defect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 8
- 208000006558 Dental Calculus Diseases 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 229910000926 A-3 tool steel Inorganic materials 0.000 description 1
- 0 CC(C)N(*)**(*)N* Chemical compound CC(C)N(*)**(*)N* 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl primary amine Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for converting mercaptan in crude oil. The method comprises the following steps of: under the condition that the molar ratio of organic amine, aldehyde and mercaptan in the crude oil is 1:(1-2):(1-2); carrying out mannich reaction, wherein the temperature is 30-150 DEG C, the pressure is 0.1-1.8MPa, and the reaction time is 0.5-2 hours; and detecting that the mercaptan does not exist. According to the method disclosed by the invention, the mercaptan is converted into macromolecule sulfocompound, and the sulfocompound is enriched in heavy oil fraction, so that the macromolecule sulfocompound can be taken as a coking-resistant antisludging agent in a high-temperature process of petroleum refining, the coking and the scaling of equipment and a pipeline can be effectively avoided, delayed and eliminated. Meanwhile, the mercaptan content in the crude oil is reduced, so that the corrosion of the mercaptan to a crude oil unit can be reduced. According to the method, the corrosive mercaptan is converted into the macromolecule sulfocompound in a pretreatment stage of the crude oil, so that the defects of the increase of equipment and investment for hydrofining can be overcome. Therefore, the method can be implemented on the basis that the equipment can not be added.
Description
Technical field
The invention belongs to the refining of petroleum field; The method for transformation that particularly relates to mercaptan in a kind of crude oil; Be used for petroleum refining process the mercaptan in the crude oil is converted into the polymer sulfocompound; This sulfocompound is enriched in the heavy oil fraction, can effectively prevent, delay the coking and fouling with abatement apparatus and pipeline as the anti-scorch Scale inhibitors of refining of petroleum pyroprocess.Simultaneously because mercaptans content reduction in the crude oil can reduce the corrosion of mercaptan to crude oil unit.
Background technology
The low molecule mercaptan that contains in the crude oil makes a kind of very niff of crude oil generation and has very strong corrodibility, makes crude oil in storage, can, transportation and the course of processing, bring very big problem.In environmental requirement more and more stricter today, press for and crude oil is carried out mercaptan removal handle.Be because: 1. mercaptan can pollute catalyzer, can reduce the use properties of fuel, obtain high-quality tank oil, needs to carry out mercaptan removal to crude oil and handles; 2. mercaptan almost all has corrodibility to all metals, in order to protect crude oil processing, storage, can and transportation equipment, should carry out mercaptan removal and handle; 3. mercaptan is a kind of individual compound, as a kind of useful raw material, should be used.
Doctor process: up to now,, normally mercaptan is changed into and be worth other less compound both at home and abroad to the doctor process that clean cargo adopted.In petroleum refining industry, one of mercaptan removal method of employing is the catalytic hydrofinishing method, and through unifining, mercaptan can change into hydrogen sulfide; Another kind method is the basic soln catalytic oxidation, under the oxygenizement of phthalocyanine catalyst, mercaptan is converted into compounds such as dialkyl group ether.As far as oil refining enterprise, the hydrotreatment clean cargo are feasible, but want unifining crude oil, and present technology is still had any problem, or because the cost height is not had an implementary value.
Research for mercaptan removal mainly is solvent extraction process at present; Extraction process clean cargo desulfurization like USP5494572; Southwest Chemical Research and Design Institute has been developed the technology that the N-N-formyl morpholine N-removes sulfide in the white oil, and these technologies mainly are to clean cargo.For crude oil, these technology can be because equipment be huge or uneconomical not obtaining implemented.
Summary of the invention
The object of the invention is the method through chemical conversion; Mercaptan in the crude oil is converted into the polymer sulfocompound; This sulfocompound is enriched in the heavy oil fraction; Can effectively prevent, delay the coking and fouling with abatement apparatus and pipeline as the anti-scorch Scale inhibitors of refining of petroleum pyroprocess.Simultaneously because mercaptans content reduction in the crude oil can reduce the corrosion of mercaptan to crude oil unit.
Just technical scheme is following in the present invention:
The method for transformation of mercaptan in a kind of crude oil, with organic amine, aldehyde, with crude oil in mercaptan be 1:1～2:1～2 in molar ratio, carry out Mannich reaction, temperature 30-150 ℃, pressure 0.1-1.8MPa, the reaction times is 0.5-2h; Detect no mercaptan.
Reaction raw materials organic amine, aldehyde advance in the crude oil unit process to add at crude oil, or add with crude oil demulsifier, make this reaction occur in crude oil and advance before the electric desalting or before crude oil advances separation column.
Mercaptan in organic amine and aldehyde and the crude oil carries out Mannich reaction, generates that to contain a kind of general structure at least be active principle suc as formula the compound of (1) or (2):
R wherein
1, R
2, R
3Be H or alkyl, R
1, R
2, R
3Be identical or different alkyl, R
1, R
2, R
3Alkyl be meant the alkyl with 1～22 carbon atom, R
4Be H or alkyl, Rx is the alkyl of carbon number 1～12.
Product (1) or (2) have anti-scorch scale effect.
Product (1) or (2) are present in the last running of crude oil, the effect of the anti-scorch scale inhibition of performance in the following process process of atmospheric pressure kiln, vacuum furnace, vacuum distillation tower and the residual oil interchanger of crude oil crude oil unit.
Product (1) or (2) get into along with vacuum residuum in the heavy oil upgrading device process of delayed coking, viscosity breaking, at the anti-scorch scale effect of system's continuation performance of interchanger, process furnace, separation column, remove, delay the high temperature service coking.
Described kiber alkyl amine is a primary t-alkyl-amine, the preferred alkyl primary amine.
The method for transformation of mercaptan in a kind of crude oil of the present invention, the product effect that its enforcement and this method generate comprises as follows:
1, organic amine, aldehyde are injected into contain in the mercaptan crude oil, in the pipeline of petroleum tank to crude oil unit, inject, preferably before crude oil pump, inject, so that mix.
The thio-alcohol material generation Mannich reaction of organic amine, aldehyde and the crude oil that 2, in the crude oil warm, is injected generates high molecular sulfocompound.
3, in primary tower, the high sulfocompound that is generated gets at the bottom of the primary tower, together gets into atmospheric pressure kiln with oil at the bottom of the primary tower, and this compound is brought into play anti-scorch scale effect in atmospheric pressure kiln, can remove, delay the atmospheric pressure kiln coking.
4, this sulfocompound gets in atmospheric tower at the bottom of the atmospheric tower, together gets into vacuum furnace with oil at the bottom of the atmospheric tower, and this compound is brought into play anti-scorch scale effect in vacuum furnace, can remove, delay the vacuum furnace coking.
5, this sulfocompound gets into VACUUM TOWER BOTTOM in vacuum distillation tower, together gets into the heavy oil interchanger with VACUUM TOWER BOTTOM oil, and this compound is brought into play anti-scorch scale effect in the heavy oil interchanger, can remove, delay the interchanger coking.
6, this sulfocompound gets into along with vacuum residuum in the heavy oil upgrading device processes such as delayed coking, viscosity breaking and can continue the anti-scorch scale effect of performance in systems such as interchanger, process furnace, separation columns, can remove, delay the high temperature service coking.
The invention has the advantages that:
The method for transformation of mercaptan in a kind of crude oil provided by the present invention; It can be by the mercaptan in organic amine, aldehyde and the crude oil through Mannich reaction; Mercaptan is converted into the polymer sulfocompound; This sulfocompound is enriched in the heavy oil fraction, can effectively prevent, delay the coking and fouling with abatement apparatus and pipeline as the anti-scorch Scale inhibitors of refining of petroleum pyroprocess.Simultaneously because mercaptans content reduction in the crude oil can reduce the corrosion of mercaptan to crude oil unit.
The present invention is converted into the polymer sulfocompound in the crude oil upgrading stage with mordant mercaptan, overcome the shortcoming of increase equipment such as unifining and investment.Therefore, the present invention can implement on the basis that does not increase equipment.
Embodiment:
Following instance is to further specify of the present invention.
Embodiment 1
To contain the normal Iranian South Pars white oil 200g of 0.1mol and pack in the 500ml four-hole bottle, add formaldehyde 0.1mol, add uncle's octadecylamine 0.1mol; On four-hole bottle, install reflux condensing tube additional, be heated to 50 ℃ of reaction 1h, reaction is reduced to room temperature after finishing; Remove bottom moisture; White oil is distilled, cut fore-running-80 ℃ with 80 ℃ of two cuts, add agent and blank sample experimental result such as table 1, table 2.
Lighting end mercaptan changing conditions before and after the Iranian South Pars white oil of table 1 mercaptan transforms
Embodiment 2
The normal Iranian South Pars white oil 200g of 0.1mol is packed in the 500ml four-hole bottle, add formaldehyde 0.2mol, add uncle's octadecylamine 0.2mol; On four-hole bottle, install reflux condensing tube additional, be heated to 150 ℃ of reaction 1h, reaction is reduced to room temperature after finishing; Remove bottom moisture; White oil is distilled, cut fore-running-80 ℃ with 80 ℃ of two cuts, add agent and blank sample experimental result such as table 3, table 4.
Lighting end mercaptan changing conditions before and after the Iranian South Pars white oil of table 3 mercaptan transforms
Embodiment 3
Vacuum residuum 300g is packed in the 500ml four-hole bottle; Add to transform back＞80 ℃ of cut 500 μ g/g respectively, add and transform preceding＞80 ℃ of cut 500 μ g/g and blank totally three groups of experiments, on four-hole bottle, install reflux condensing tube additional; In oil, add the test piece of A3 steel; After being heated to 400 ℃ of constant temperature 24h, test piece is taken out with weighing anti-tartar experimental result such as table 5 after the petroleum ether.
Table 5 anti-tartar experimental result
Can find out that by table 5 behind the heavy distillate after adding mercaptan transforms in the vacuum residuum, the anti-tartar rate is greater than 50%.
Embodiment 4
Cycle oil slurry samples 300g is packed in the 500ml four-hole bottle; Add to transform back＞80 ℃ of cut 200 μ g/g respectively, add and transform preceding＞80 ℃ of cut 200 μ g/g and blank totally three groups of experiments, on four-hole bottle, install reflux condensing tube additional; Under stirring state; After being heated to 290 ℃ of constant temperature 24h, the kinematic viscosity of working sample, anti-tartar experimental result such as table 6.
Table 6 anti-tartar experimental result
Can find out that by table 6 behind the heavy distillate after adding mercaptan transforms in the catalytically cracked oil, the anti-tartar rate is greater than 30%.
Claims (6)
1. the method for transformation of mercaptan in the crude oil is characterized in that: with organic amine, aldehyde, with crude oil in mercaptan be 1:1～2:1～2 in molar ratio, carry out Mannich reaction, temperature 30-150 ℃, pressure 0.1-1.8MPa, the reaction times is 0.5-2h; Detect no mercaptan.
2. the method for claim 1 is characterized in that reaction raw materials organic amine, aldehyde advance in the crude oil unit process to add at crude oil, or adds with crude oil demulsifier, makes this reaction occur in crude oil and advances before the electric desalting or before crude oil advances separation column.
3. the method for claim 1 is characterized in that the mercaptan in organic amine and aldehyde and the crude oil carries out Mannich reaction, generates that to contain a kind of general structure at least be active principle suc as formula the compound of (1) or (2):
R wherein
1, R
2, R
3Be H or alkyl, R
1, R
2, R
3Be identical or different alkyl, R
1, R
2, R
3Alkyl be meant the alkyl with 1～22 carbon atom, R
4Be H or alkyl, Rx is the alkyl of carbon number 1～12.
4. the method for claim 1 is characterized in that described organic amine is a kiber alkyl amine.
5. method as claimed in claim 4 is characterized in that described kiber alkyl amine is a primary t-alkyl-amine.
6. the method for claim 1 is characterized in that described aldehyde is formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102230117A CN102719268A (en) | 2012-06-28 | 2012-06-28 | Method for converting mercaptan in crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102230117A CN102719268A (en) | 2012-06-28 | 2012-06-28 | Method for converting mercaptan in crude oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102719268A true CN102719268A (en) | 2012-10-10 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102230117A Pending CN102719268A (en) | 2012-06-28 | 2012-06-28 | Method for converting mercaptan in crude oil |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666564A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Antiscale composition and application thereof |
| CN113740334A (en) * | 2021-08-17 | 2021-12-03 | 中国石油大学(华东) | Heavy oil green coke form in-situ characterization device and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB735784A (en) * | 1952-07-03 | 1955-08-31 | Exxon Standard Sa | Process for removing mercaptans from hydrocarbon fractions |
| CN1583974A (en) * | 2003-08-20 | 2005-02-23 | 中国石油化工股份有限公司 | Method for decreasing sulfur content of distillate |
| CN101597514A (en) * | 2009-06-26 | 2009-12-09 | 天津汇荣石油有限公司 | A kind of technology of crude oil upgrading and reactant thereof |
-
2012
- 2012-06-28 CN CN2012102230117A patent/CN102719268A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB735784A (en) * | 1952-07-03 | 1955-08-31 | Exxon Standard Sa | Process for removing mercaptans from hydrocarbon fractions |
| CN1583974A (en) * | 2003-08-20 | 2005-02-23 | 中国石油化工股份有限公司 | Method for decreasing sulfur content of distillate |
| CN101597514A (en) * | 2009-06-26 | 2009-12-09 | 天津汇荣石油有限公司 | A kind of technology of crude oil upgrading and reactant thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666564A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Antiscale composition and application thereof |
| CN103666564B (en) * | 2012-09-26 | 2015-07-01 | 中国石油化工股份有限公司 | Antiscale composition and application thereof |
| CN113740334A (en) * | 2021-08-17 | 2021-12-03 | 中国石油大学(华东) | Heavy oil green coke form in-situ characterization device and method |
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Application publication date: 20121010 |