CN102373067B - Method for preventing salt coagulation of fractionating tower - Google Patents
Method for preventing salt coagulation of fractionating tower Download PDFInfo
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- CN102373067B CN102373067B CN 201010256536 CN201010256536A CN102373067B CN 102373067 B CN102373067 B CN 102373067B CN 201010256536 CN201010256536 CN 201010256536 CN 201010256536 A CN201010256536 A CN 201010256536A CN 102373067 B CN102373067 B CN 102373067B
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Abstract
The invention discloses a method for preventing salt coagulation of a fractionating tower so as to overcome the disadvantages of great time consumption, equipment stop or yield decrease as well as hidden corrosion dangers in prior art. The method comprises the steps of: adding a salt coagulation inhibitor to a rich absorption oil pipeline of a fractionating tower or a diesel stripping tower overhead refluxing pipeline continuously, with an adding amount of 3-10mg/kg of the oil flow in the rich absorption oil pipeline of the fractionating tower or in the diesel stripping tower overhead refluxing pipeline. The salt coagulation inhibitor is composed of 30-70 wt% of an aliphatic nitrogen compound, 10-30 wt% of alkyl alcohol and 20-40 wt% of an organic solvent.
Description
Technical field
The bright oil refining apparatus corrosion control field that belongs to of this law more particularly relates to a kind of method that prevents the oil refining apparatus salt crust, is specially adapted to prevent the ammonium salt fouling corrosion of catalytic cracking unit and delayed coking unit separation column.
Background technology
In recent years along with the development trend of crude oil heaviness, poor qualityization, and market is to the significantly rising of light-end products demand, and the crude oil deep processing becomes the main direction of oil refining industry development.Wherein heavy oil fluid catalytic cracking and delay coking process more and more obtain the extensive attention of oil refining industry as the main means of heavy oil lighting.Contain assorted elements such as higher N, S, O, Cl in delayed coking unit or the heavy oil catalytically cracking equipment raw material, reaction at high temperature is easy to generate NH
3, H
2The heat absorption hydrolysis reaction takes place in products such as S, butter and organic chloride, decomposes to produce HCl.The gas phase NH that follows raw material to respond and generate
3And HCl, hybrid reaction oil gas enters separation column.Along with the rising of oil gas in separation column, temperature also has high step-down in the tower, when temperature is down to 330 ℃ of left and right sides, and NH
3Be combined with HCl and generate NH
4Cl, NH
4Cl is carried to the upper strata tower tray with superfine little particle by oil gas, when temperature is down to about 140 ℃ and is followed oil gas continue to rise and temperature when constantly descending, and NH in the oil gas
4Cl concentrates dehydration and becomes crystal, mixes with impurity such as iron rust, coke powder powder and is deposited on tower tray, downtake, is subjected to liquid bath, extracts pipeline, trim the top of column line and the pump housing etc. out and locate.Salt crust can hinder flowing of oil gas when light, causes the separation column pressure drop to increase gradually behind the obstruction tower tray, destroys the normal running of separation column, influences the oil separating effect; Cause towards tower and flooding when serious, make operation disorderly, even occluding device is to produce normally to move.While NH
4The salt crust of Cl causes serious underdeposit corrosion to equipment.
Salt crust for fractionator overhead tower tray and trim the top of column line, domestic delayed coking unit and catalytic cracking unit separation column substantially all are the methods that adopts washing to handle, the principle of washing is exactly that water dissolves the solid ammonium salt, take ammonium salt out of separation column by the aqueous solution, though the details of washing is slightly different, for example some uses deaerated water, and some uses fresh water, but washing principle and flow process are roughly the same.Handle the main promising shut-down washing of washing process and the online washing of separation column salt crust, the washing of stopping work needs to cut off charging, and this flow process is the separation column outer circulation, is washed by the separation column crestal waterflood then, and this method is not only time-consuming but also lose bigger; When handling, online washing needs to reduce earlier the raw material amount of finish; strengthen separation column cold reflux and top quantity of reflux then; tower top temperature is reduced; and squeeze into a certain amount of cold reflux fresh water with the cat head recycle pump in outlet; fresh water and cat head turning oil are mixed into separation column; the salt crust at positions such as flushing and dissolving tower tray, downtake; washing water and partial reflux distillate then extracts out through the cat head recycle pump; entering the raw gasline jar then separates; this method is taken light cycle oil in the oily(waste)water to through regular meeting, and the NH that dissolves in water washing process
4Cl flows to down one deck tower tray with the liquid-phase reflux in the tower, raises gradually with temperature, causes the salt crust position to move down easily and can not eliminate salt crust fully.In addition the washing treating processes in, NH
4The Cl aqueous solution has stronger corrodibility to equipment and pipeline, causes the heavy corrosion of equipment after assemble at the lower position of flow velocity.
" contemporary chemical industry ", 2004, a kind of method of handling salt crust of washing is disclosed in 33 (4), it is at the separation column of salt crust, by reducing the method for fractionator overhead temperature, increasing steam condensate and fresh water, salt crust on dissolving wash tray and the downtake, recovery operation rapidly alleviates financial loss.Also can prevent the generation of separation column salt crust in addition by the method for strengthening electric desalting operation and the design of improvement separation column.This technology is the improvement on water washing treatment method, can handle separation column salt crust problem under not shut-down situation.But this method need the amount of falling, reduce fractionation cat head temperature, and has underdeposit corrosion hidden danger.
" oil Refining Technologies and engineering " discloses a kind of method of handling salt crust of washing in 2009,39 (3), and it is the situation at delayed coking unit separation column head tower dish salt crust, points out that online washing is comparatively effectively solution of separation column head tower dish salt crust.Can push up the measures such as returning the tower temperature that circulates and prevent separation column salt crust problem by guaranteeing original desalting effect, suitable by-passing portions top turning oil, control in addition.But this technology is traditional water washing treatment method, and separation column stops charging in the treating processes, cooling washing, and complex disposal process.
Summary of the invention
The purpose of this invention is to provide a kind of method that prevents catalytic cracking unit and delayed coking unit separation column salt crust.This method has been avoided the generation of catalytic cracking unit and delayed coking unit separation column salt crust phenomenon, has easy and simple to handle, safety and saves time, reduces advantage such as financial loss.
The invention provides a kind of method that prevents the separation column salt crust, it is characterized in that: add a kind of salt crust inhibitor continuously at separation column rich absorbent oil pipeline, the salt crust inhibitor with enter separation column after oil product in the separation column rich absorbent oil pipeline mixes, the injection rate of salt crust inhibitor is 3～10mg/kg of oil product flow in the separation column rich absorbent oil pipeline.
The invention provides the method that another kind prevents the separation column salt crust, it is characterized in that: the diesel oil stripping cat head return wire at separation column adds a kind of salt crust inhibitor continuously, the salt crust inhibitor with enter separation column after oil product in the diesel oil stripping cat head return wire mixes, the injection rate of salt crust inhibitor is 3～10mg/kg of oil product flow in the diesel oil stripping cat head return wire.
The invention provides the method that another kind prevents the separation column salt crust, it is characterized in that: rich absorbent oil pipeline and diesel oil stripping cat head return wire at separation column add a kind of salt crust inhibitor continuously, the salt crust inhibitor with enter separation column after oil product in rich absorbent oil pipeline and the diesel oil stripping cat head return wire mixes, the add-on of salt crust inhibitor is 3～10mg/kg of oil product flow in rich absorbent oil pipeline and the diesel oil stripping cat head return wire.
The inhibitor of salt crust described in the present invention is made up of following component:
(A) 30～70 weight % fat nitrogenous compound, preferred content is 50～65 weight %;
(B) 10～30 weight % alkyl alcohols, preferred content is 15～25 weight %;
(C) 20～40 weight % organic solvents, preferred content is 20～30 weight %.
In salt crust inhibitor gross weight.
Fatty nitrogenous compound described in the present invention is C
6～C
18In the aliphatic amide any one or two kinds, preferred C
8～C
12In the aliphatic amide any one or two kinds.
Alkyl alcohol described in the present invention is C
3～C
5Any one or two kinds in alkyl monocarbon alcohol or the dibasic alcohol.
Organic solvent described in the present invention is C
7～C
12Any one or two kinds in the aromatic hydrocarbons.
Inhibitor of the present invention adopts the mode of former dose of injection.
The inventive method can be used for preventing ammonium salt fouling and the corrosion in the oil refining apparatus, mainly for the treatment of fouling and the etching problem of the chlorination ammonium salt in catalytic cracking unit and the delayed coking unit separation column.
The present invention handles separation column salt crust technology with present washing and compares, and has the following advantages: (1) the present invention has that execute-in-place is easy, safety saves time and advantage with low cost, has avoided water washing treatment method time-consuming, the shortcoming that the amount of falling or device are stopped work.(2) the present invention generates oil soluble salt by inhibitor and HCl, suppresses the generation of ammonium chloride, thereby prevents that fouling and the etching problem of ammonium chloride from appearring in separation column, to guarantee the separation column normal running.
Describe the present invention in detail with the drawings and specific embodiments below, but do not limit the scope of the invention.
Accompanying drawing and description of drawings
Fig. 1 is a kind of method flow sketch that prevents the separation column salt crust of the present invention.
Fig. 2 prevents the method flow sketch of separation column salt crust for another kind of the present invention.
Among the figure:
1-salt crust inhibitor, 2-rich absorbent oil pipeline, 3-diesel oil stripping cat head return wire, 4-separation column, 5-distillate.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but these embodiment do not limit the scope of the invention.
As shown in Figure 1, salt crust inhibitor 1 joins rich absorbent oil pipeline 2, add-on is 3～10mg/kg of oil product flow in the rich absorbent oil pipeline 2 of separation column 4, salt crust inhibitor 1 mixes with rich absorbent oil in the rich absorbent oil pipeline 2, enter separation column 4, salt crust inhibitor 1 flows to the upper strata of tower with the vapour phase in the tower, active ingredient fat nitrogenous compound and HCl generation oil soluble salt in the salt crust inhibitor 1 in flow process, be dissolved in the distillate 5 of corresponding boiling range, thereby stop NH
3Be combined with HCl and generate NH
4Cl takes separation column out of with distillate 5 then.
As shown in Figure 2, salt crust inhibitor 1 joins in the diesel oil stripping cat head return wire 3, add-on is 3～10mg/kg of oil product flow in the diesel oil stripping cat head return wire 3, salt crust inhibitor 1 mixes with the stripping tower trimming oil, enter separation column 4, salt crust inhibitor 1 flows to the upper strata of tower with the vapour phase in the tower, and salt crust inhibitor 1 active ingredient fat nitrogenous compound and HCl generate oil soluble salt in flow process, be dissolved in the distillate of corresponding boiling range, thereby stop NH
3Be combined with HCl and generate NH
4Cl takes separation column 4 out of with distillate 5 then.
Present embodiment is the inhibition ability of test salt crust inhibitor to ammonium chloride crystals salt.In three mouthfuls of Florence flasks of a 200mL, add 100 certain refinery catalytic gasoline of gram, the character of catalytic gasoline is as shown in table 1, add 1 gram chloride solid powder then, in 50 ℃ of water-baths, slowly stir, observe the chloride solid powder deposition at drag after stopping after 30 minutes stirring.Slowly dripping 1.5 gram proportionings in the catalytic gasoline with dropper is amino dodecane: rare five amine of tetrem: propyl carbinol: heavy aromatics=30: 35: 15: 20 salt crust inhibitor of the present invention, slowly stir and find that the chloride solid powder fades away, and in gasoline, observed bubble and overflowed, stopped stirring the completely dissolve of discovery chloride solid powder after 5 minutes.
The character of table 1 catalytic gasoline
| Catalytic gasoline | Density, g/cm 3 | Sulphur, μ g/g | Nitrogen, μ g/g | Colloid, mg/100mL |
| Before the inhibiting | 0.7224 | 502 | 185 | 1.5 |
| After the inhibiting | 0.7226 | 498 | 1260 | 1.5 |
Embodiment 2
Certain refinery delayed coking unit, it is bigger that the top circular wave often appears in coking fractional distillation column, and the top is followed the frequent discontinuity of pump and is found time, and the tower top temperature fluctuation is bigger, and raw gasline is done rising, and is black; Average 1 first quarter moon need be washed processing once generally speaking, add a kind of salt crust inhibitor at diesel oil stripping cat head return wire, the proportioning of salt crust inhibitor is octodrine: amino dodecane: propyl carbinol: heavy aromatics=30: 30: 20: 20, add-on is 8mg/kg, the separation column smooth operation, unusual phenomenon do not occur, all indexs all do not have and exceed standard.The character of adding salt crust inhibitor front and back coker gasoline is as shown in table 2.
Table 2 adds the character of salt crust inhibitor front and back coker gasoline
| Catalytic gasoline | Density, g/cm 3 | Sulphur, μ g/g | Nitrogen, μ g/g | Colloid, mg/100mL |
| Before the inhibiting | 0.7340 | 543 | 204 | 1.6 |
| After the inhibiting | 0.7298 | 538 | 210 | 1.6 |
Embodiment 3
Certain refinery heavy oil catalytically cracking equipment, separation column salt crust problem often appears, plate pressure drop increases, it is bigger that gasoline products is done fluctuating range, needs washing in average per 2 months is handled once, add the salt crust inhibitor at separation column rich absorbent oil pipeline, salt crust inhibitor proportioning is amino dodecane: rare five amine of tetrem: propyl carbinol: heavy aromatics=30: 35: 15: 20, the add-on of salt crust inhibitor is 8mg/kg in the separation column rich absorbent oil pipeline, the separation column smooth operation, unusual phenomenon do not occur, all indexs all do not have and exceed standard.The character of adding salt crust inhibitor front and back catalytic gasoline is as shown in table 3.
Table 3 adds the character of salt crust inhibitor front and back catalytic gasoline
| Catalytic gasoline | Density, g/cm 3 | Sulphur, μ g/g | Nitrogen, μ g/g | Colloid,, mg/100mL |
| Before the inhibiting | 0.7218 | 482 | 178 | 1.5 |
| After the inhibiting | 0.7215 | 475 | 183 | 1.5 |
Claims (9)
1. method that prevents the separation column salt crust, it is characterized in that: add a kind of salt crust inhibitor continuously at separation column rich absorbent oil pipeline, the salt crust inhibitor with enter separation column after oil product in the separation column rich absorbent oil pipeline mixes, the add-on of salt crust inhibitor is 3～10mg/kg of oil product flow in the separation column rich absorbent oil pipeline, and wherein said salt crust inhibitor is made up of following component:
(A) 30～70 weight % fat nitrogenous compound;
(B) 10～30 weight % alkyl alcohols;
(C) 20～40 weight % organic solvents;
In salt crust inhibitor gross weight, wherein said fatty nitrogenous compound is C
6～C
18In the aliphatic amide any one or two kinds, alkyl alcohol is C
3～C
5Any one or two kinds in alkyl monocarbon alcohol or the dibasic alcohol, organic solvent is C
7～C
12Any one or two kinds in the aromatic hydrocarbons.
2. method according to claim 1, it is characterized in that: described fatty nitrogenous compound is C
8～C
12In the aliphatic amide any one or two kinds.
3. method according to claim 1, it is characterized in that: the content of described fatty nitrogenous compound is 50～65 weight %, and the content of alkyl alcohol is 15～25 weight %, and the content of organic solvent is 20～30 weight %, in salt crust inhibitor gross weight.
4. method that prevents the separation column salt crust, it is characterized in that: the diesel oil stripping cat head return wire at separation column adds a kind of salt crust inhibitor continuously, the salt crust inhibitor with enter separation column after oil product in the diesel oil stripping cat head return wire mixes, the add-on of salt crust inhibitor is 3～10mg/kg of oil product flow in the diesel oil stripping cat head return wire, and wherein said salt crust inhibitor is made up of following component:
(A) 30～70 weight % fat nitrogenous compound;
(B) 10～30 weight % alkyl alcohols;
(C) 20～40 weight % organic solvents;
In salt crust inhibitor gross weight, wherein said fatty nitrogenous compound is C
6～C
18In the aliphatic amide any one or two kinds, alkyl alcohol is C
3～C
5Any one or two kinds in alkyl monocarbon alcohol or the dibasic alcohol, organic solvent is C
7～C
12Any one or two kinds in the aromatic hydrocarbons.
5. method according to claim 4, it is characterized in that: described fatty nitrogenous compound is C
8～C
12In the aliphatic amide any one or two kinds.
6. method according to claim 4, it is characterized in that: the content of described fatty nitrogenous compound is 50～65 weight %, and the content of alkyl alcohol is 15～25 weight %, and the content of organic solvent is 20～30 weight %, in salt crust inhibitor gross weight.
7. method that prevents the separation column salt crust, it is characterized in that: rich absorbent oil pipeline and diesel oil stripping cat head return wire at separation column add a kind of salt crust inhibitor continuously, the salt crust inhibitor with enter separation column after oil product in rich absorbent oil pipeline and the diesel oil stripping cat head return wire mixes, the add-on of salt crust inhibitor is 3～10mg/kg of oil product flow in rich absorbent oil pipeline and the diesel oil stripping cat head return wire, and wherein said salt crust inhibitor is made up of following component:
(A) 30～70 weight % fat nitrogenous compound;
(B) 10～30 weight % alkyl alcohols;
(C) 20～40 weight % organic solvents;
In salt crust inhibitor gross weight; Described fatty nitrogenous compound is C
6～C
18In the aliphatic amide any one or two kinds, alkyl alcohol is C
3～C
5Any one or two kinds in alkyl monocarbon alcohol or the dibasic alcohol, organic solvent is C
7～C
12Any one or two kinds in the aromatic hydrocarbons.
8. method according to claim 7, it is characterized in that: described fatty nitrogenous compound is C
8～C
12In the aliphatic amide any one or two kinds.
9. method according to claim 7, it is characterized in that: the content of described fatty nitrogenous compound is 50～65 weight %, and the content of alkyl alcohol is 15～25 weight %, and the content of organic solvent is 20～30 weight %, in salt crust inhibitor gross weight.
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|---|---|---|---|
| CN 201010256536 CN102373067B (en) | 2010-08-19 | 2010-08-19 | Method for preventing salt coagulation of fractionating tower |
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|---|---|---|---|
| CN 201010256536 CN102373067B (en) | 2010-08-19 | 2010-08-19 | Method for preventing salt coagulation of fractionating tower |
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| CN102373067B true CN102373067B (en) | 2013-09-11 |
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| CN102703114A (en) * | 2012-05-28 | 2012-10-03 | 李小燕 | Method for preventing fractionating tower from salt deposition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754944A (en) * | 2004-09-29 | 2006-04-05 | 上海贵通新材料科技有限公司 | Corrosion inhibitor for hydrogenation plant |
| CN101705112A (en) * | 2009-11-12 | 2010-05-12 | 沈阳工业大学 | Water-soluble imidazoline amide corrosion inhibitor, preparation method thereof and using method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754944A (en) * | 2004-09-29 | 2006-04-05 | 上海贵通新材料科技有限公司 | Corrosion inhibitor for hydrogenation plant |
| CN101705112A (en) * | 2009-11-12 | 2010-05-12 | 沈阳工业大学 | Water-soluble imidazoline amide corrosion inhibitor, preparation method thereof and using method thereof |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant after: Sinopec Corp. Co-applicant after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant before: Sinopec Corp. Co-applicant before: Luoyang Petrochemical Engineering Co., China Petrochemical Group |
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