CN103805274A - Liquefied gas desulfurization refining device and liquefied gas desulfurization refining method in oil refinery - Google Patents

Liquefied gas desulfurization refining device and liquefied gas desulfurization refining method in oil refinery Download PDF

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CN103805274A
CN103805274A CN201410077771.0A CN201410077771A CN103805274A CN 103805274 A CN103805274 A CN 103805274A CN 201410077771 A CN201410077771 A CN 201410077771A CN 103805274 A CN103805274 A CN 103805274A
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tank
liquefied gas
fiber
extracting slurry
slurry tank
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CN201410077771.0A
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Chinese (zh)
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CN103805274B (en
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周建文
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中国石油化工股份有限公司
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Abstract

The invention relates to a liquefied gas desulfurization refining device in an oil refinery. The device comprises a buffer tank, an extraction tower, an MDEA (methyldiethanolamine) solvent storage tank, an alkaline liquor storage tank, a water storage tank, a primary extraction settling tank, a secondary extraction settling tank and a tertiary extraction settling tank, wherein the outlet of the buffer tank is connected with the bottom inlet of the extraction tower; the top outlet of the extraction tower is connected to the primary extraction settling tank by virtue of a coalescer and a primary fiber membrane contactor; the MDEA solvent storage tank is respectively communicated with the upper outlet of the extraction tower and the primary fiber membrane contactor; a top outlet of the primary extraction settling tank is connected to the secondary extraction settling tank by virtue of a secondary fiber membrane contactor; the top outlet of the secondary extraction settling tank is connected to the tertiary extraction settling tank by virtue of a tertiary fiber membrane contactor; the alkaline liquor storage tank is respectively communicated with the secondary fiber membrane contactor and the tertiary fiber membrane contactor; the water storage tank is communicated with the tertiary fiber membrane contactor. According to the device, when the liquefied gas is subjected to desulfurization refining, the desulfurization effect is good, the consumption of the solvent and alkaline liquor is low, and the cost is greatly saved.

Description

A kind of device and method of oil refinery liquefied gas desulfuration purification
Technical field
The present invention relates to a kind of device and method of oil refinery liquefied gas desulfuration purification, is the improvement to the existing liquefied gas desulfurizing and refining method of refinery.
Background technology
Oil refinery liquefied gas is mainly derived from the devices such as catalytic cracking, delayed coking, normal decompression, hydrocracking, CONTINUOUS REFORMER, its main ingredient is carbon three, carbon four hydrocarbon, containing a small amount of carbon two, carbon five hydro carbons, also contain hydrogen sulfide (approximately 0.01 ~ 4%), mercaptan (approximately 1 ~ 9000 mg/m 3), thioether (0 ~ 100 mg/m 3), COS sulfides.
Refinery's liquefied gas is different with component because of its source, and each sulfide content difference is very large, but is mainly hydrogen sulfide and mercaptan.The liquefied gas of normal decompression, hydrocracking, continuous reformer because of olefin(e) centent few, major part is the stable hydrocarbon such as propane, butane, as civil liquefied gas, the total sulfur after refining meets and is not more than 343mg/m 3; If the industrial chemicals as downstream unit is as produced propane, normal butane, Trimethylmethane etc., total sulfur is controlled at 100mg/m conventionally 3below, certainly more low better; And propylene, the iso-butylene of the liquefied gas of catalysis, coker product because containing high added value, in order to meet gas separation unit separation of propylene, propane and carbon four, (iso-butylene in carbon four can be used as the raw material of MTBE device, MTBE chemistry methyl tertiary butyl ether by name, the blend component of producing stop bracket gasoline) specification of quality, total sulfur in liquefied refinery gas must be removed and is less than 100mg/m 3below.
What refinery adopted conventionally at present is in extraction tower, to use N methyldiethanol amine (MDEA) solvent depriving hydrogen sulphide, and adopt the method for two-stage alkali cleaning to remove mercaptan, because liquefied gas source is assorted, the liquefied gas that particularly catalysis, coker are produced is with coke powder, adopt MDEA solvent to carry out in desulfuration of liquefied gas hydrogen process at extraction tower, easily cause column plate or filler to stop up, cause on the one hand and remove hydrogen sulfide effect decline in liquefied gas, in extracting tower top liquefied gas, greatly, far away surpassing is not more than 20mg/m in hydrogen sulfide fluctuation 3quality control, increased the consumption of caustic washing system alkali lye; Extracting tower top liquefied gas is carried MDEA solvent secretly to liquefied gas caustic washing system on the other hand, causes the COD in alkaline residue high, makes in follow-up alkaline residue and the anhydrate activity of active sludge for the treatment of unit processing of water declines, and affect refinery water quality and discharges.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, a kind of device and method of oil refinery liquefied gas desulfuration purification is provided, and while utilizing this device to carry out desulfuration purification to liquefied gas, sweetening effectiveness is good, and solvent and alkali lye consumption are low, have greatly saved cost.
Technical scheme of the present invention is:
A kind of device of oil refinery liquefied gas desulfuration purification, comprise surge tank, extraction tower, MDEA solvent tank, alkali lye storage tank, water storage tank, one-level extracting slurry tank, secondary extracting slurry tank and three grades of extracting slurry tanks, surge tank outlet is connected with extraction tower bottom inlet, extraction tower top exit is connected to one-level extracting slurry tank by coalescer and one-level fiber-film contact, MDEA solvent tank is communicated with extraction tower upper entrance and one-level fiber-film contact respectively, one-level extracting slurry tank top exit is connected to secondary extracting slurry tank by secondary fiber-film contact, secondary extracting slurry tank top exit is connected to three grades of extracting slurry tanks by three grades of fiber-film contacts, alkali lye storage tank is communicated with secondary fiber-film contact and three grades of fiber-film contacts respectively, water storage tank is communicated with three grades of fiber-film contacts.
Utilize said apparatus oil refinery liquefied gas to be carried out to the method for desulfuration purification, comprise the steps:
(1) by until refining liquefied gas after surge tank buffering, with MDEA solvent counter current contact in extraction tower, the rich solution that discharge extraction tower bottom goes regenerator column regeneration to reach recycle, the liquefied gas that extracting tower top is discharged is after coalescer is removed impurity, enter into one-level extracting slurry tank by one-level fiber-film contact, fully contact with MDEA solvent; The present invention utilizes the feature that one-level extracting slurry tank fiber-film contact contact area is large, hydrocarbon phase separates with water compatible free settling, and the solvent that liquefied gas extraction tower is caused because of the dirty easy obstruction of raw material liquefied gas runs to damage and reclaims and utilize in first step extracting slurry tank.
(2) rich solution of discharging from one-level extracting slurry tank bottom goes regenerator column regeneration to reach recycle, and the liquefied gas of discharging from one-level extracting slurry tank top enters secondary extracting slurry tank by secondary fiber-film contact, fully contacts with alkali lye;
(3) alkali lye of discharging from secondary extracting slurry tank bottom recycles, the liquefied gas of discharging from secondary extracting slurry tank top enters three grades of extracting slurry tanks by three grades of fiber-film contacts, fully contact with alkali lye or water, from the liquefied gas purification that is of three grades of extracting slurry tank tops discharges.At third stage extracting slurry tank, it operates the requirement of visual liquefied refinery gas total sulfur and can wash, and also can further reduce liquefied gas total sulfur with alkali cleaning, meets the quality control requirement of liquefied gas desulfurizing and refining total sulfur.
In step (1), the aqueous solution that described MDEA solvent is MDEA, mass concentration is 20 ~ 50%.
In step (2), described alkali lye is sodium hydroxide solution, and mass concentration is 10 ~ 30%.
Beneficial effect of the present invention: the improvement of this technique has guaranteed that the solvent that solvent tower is carried secretly is recycled utilization, guarantee that again liquefied gas removes hydrogen sulfide qualified, reduce the consumption of solvent and alkali lye, third stage fiber-film contact of the present invention both can be with washing depending on the control of liquefied gas total sulfur, also can further reduce liquefied gas total sulfur with alkali cleaning, meet the quality control requirement of liquefied gas desulfurizing and refining total sulfur.Adopt existing conventional desulfuration of liquefied gas technology, in extraction tower, use MDEA solvent extraction to remove hydrogen sulfide, then adopt two-stage alkali cleaning to add the method for one-level water elution except mercaptan, the content of the liquefied gas hydrogen sulfide that extraction tower goes out is 14.2mg/m 3~3124 mg/m 3, guaranteeing the de-rear total sulfur≤30mg/m of refining liquid hydrocarbon after alkali cleaning 3under, MDEA solvent-oil ratio is about 0.274kg/t, and alkali lye consumption is about 8.19 kg/t, adopts after treatment process of the present invention, and the content that carries out liquefied gas hydrogen sulfide after treatment with MDEA solvent in extraction tower and one-level extracting slurry tank is lower than 14.2mg/m 3, after alkali cleaning, refining liquid hydrocarbon reaches total sulfur≤30mg/m after taking off 3under, and MDEA solvent-oil ratio is about 0.115kg/t, alkali lye consumption is about 3.11 kg/t.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of liquefied gas desulfurizing and refining device of the present invention.
Wherein, 1-surge tank, 2-extraction tower, 3-coalescer, 4-one-level fiber-film contact, 5-one-level extracting slurry tank, 6-secondary fiber-film contact, 7-secondary extracting slurry tank, tri-grades of fiber-film contacts of 8-, tri-grades of extracting slurry tanks of 9-, 10-alkali lye storage tank, 11-water storage tank.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
As shown in Figure 1, Fig. 1 is the schematic diagram of liquefied gas desulfurizing and refining device of the present invention, liquefied gas desulfurizing and refining device of the present invention, comprise surge tank 1, extraction tower 2, MDEA solvent tank 12, alkali lye storage tank 10, water storage tank 11, one-level extracting slurry tank 5, secondary extracting slurry tank 7 and three grades of extracting slurry tanks 9, surge tank 1 outlet is connected with extraction tower 2 bottom inlets, extraction tower 2 top exits are connected to one-level extracting slurry tank 5 by coalescer 3 and one-level fiber-film contact 4, MDEA solvent tank 12 is communicated with extraction tower 2 upper entrances and one-level fiber-film contact 4 respectively, one-level extracting slurry tank 5 top exits are connected to secondary extracting slurry tank 7 by secondary fiber-film contact 6, secondary extracting slurry tank 7 top exits are connected to three grades of extracting slurry tanks 9 by three grades of fiber-film contacts 8, alkali lye storage tank 10 is communicated with secondary fiber-film contact 6 and three grades of fiber-film contacts 8 respectively, water storage tank 11 is communicated with three grades of fiber-film contacts 8.
For the effect of test process modification of the present invention, utilize said apparatus to test on the III of Jinling Petrochemical Co. catalytic liquefaction desulfurization is refining: by until refining liquefied gas after surge tank 1 cushions, with MDEA solvent in the interior counter current contact of extraction tower 2, the rich solution that discharge extraction tower 2 bottoms goes regenerator column to reach recycle, the liquefied gas that discharge on extraction tower 2 tops is removed after impurity through coalescer 3, enter into one-level extracting slurry tank 5 by one-level fiber-film contact 4, fully contact with MDEA solvent, MDEA solvent quality concentration is 30%; The rich solution of discharging from one-level extracting slurry tank 5 bottoms goes regenerator column to reach recycle, the liquefied gas of discharging from one-level extracting slurry tank 5 tops enters secondary extracting slurry tank 7 by secondary fiber-film contact 6, fully contact with alkali lye, alkali lye is that mass concentration is 20% aqueous sodium hydroxide solution; The alkali liquid regeneration of discharging from secondary extracting slurry tank 7 bottoms, recycle, the liquefied gas of discharging from secondary extracting slurry tank 7 tops enters three grades of extracting slurry tanks 9 by three grades of fiber-film contacts 8, fully contact with alkali lye or water depending on liquefied refinery gas total sulfur requirement control, from the liquefied gas purification that is of three grades of extracting slurry tank tops discharges.
What before the III of Jinling Petrochemical Co. catalytic liquefaction desulfurization is refining, adopt is the desulfuration purification device of existing conventional desulfuration of liquefied gas technology, in extraction tower, use MDEA solvent extraction to remove hydrogen sulfide, then adopt two-stage alkali cleaning to add the method for one-level water elution except mercaptan.
From result of use, liquefied gas treatment capacity is under 65~80t/h, and process thionizer and primary amine are washed postcure hydrogen and substantially removed, by 14.2mg/m before improving 3~3124 mg/m 3be reduced to and be less than 14.2 mg/m 3, reduce solvent and run damage in alkaline residue, avoid alkaline residue processing pipeline to stop up, MDEA solvent consumption is reduced to 8.45 tons/month by 20 tons/month, and MDEA solvent unit consumption is reduced to 0.115kg/t by 0.274kg/t, and alkali lye consumption is total sulfur≤30mg/m after assurance liquid hydrocarbon is de- 3under, being reduced to 6t/ days by 16t/ days in the past (on average), alkaline residue discharge capacity is reduced to 7.4t/ days by improving front 19t/ days (on average).Reduce thus 5 tons of/month * 1.85 ten thousand yuan/ton=9.25 ten thousand yuan of solvent consumptions, save 300 tons of/month * 700 yuan/ton * 10 of alkali lye -4=21 ten thousand yuan, by 200 yuan/ton of alkaline residue processing costs, save the about 11.6*30*200*10 of processing cost -4=6.96 ten thousand yuan/month, approximately 37.21 ten thousand yuan/month of total economic benefits, environmental benefit is remarkable.

Claims (4)

1. the device of an oil refinery liquefied gas desulfuration purification, it is characterized in that, comprise surge tank, extraction tower, MDEA solvent tank, alkali lye storage tank, water storage tank, one-level extracting slurry tank, secondary extracting slurry tank and three grades of extracting slurry tanks, surge tank outlet is connected with extraction tower bottom inlet, extraction tower top exit is connected to one-level extracting slurry tank by coalescer and one-level fiber-film contact, MDEA solvent tank is communicated with extraction tower upper entrance and one-level fiber-film contact respectively, one-level extracting slurry tank top exit is connected to secondary extracting slurry tank by secondary fiber-film contact, secondary extracting slurry tank top exit is connected to three grades of extracting slurry tanks by three grades of fiber-film contacts, alkali lye storage tank is communicated with secondary fiber-film contact and three grades of fiber-film contacts respectively, water storage tank is communicated with three grades of fiber-film contacts.
2. utilize said apparatus oil refinery liquefied gas to be carried out to the method for desulfuration purification, it is characterized in that, comprise the steps:
(1) by until refining liquefied gas after surge tank buffering, with MDEA solvent counter current contact in extraction tower, the rich solution that discharge extraction tower bottom goes regenerator column regeneration to reach recycle, the liquefied gas that extracting tower top is discharged is after coalescer is removed impurity, enter into one-level extracting slurry tank by one-level fiber-film contact, fully contact with MDEA solvent;
(2) rich solution of discharging from one-level extracting slurry tank bottom goes regenerator column regeneration to reach recycle, and the liquefied gas of discharging from one-level extracting slurry tank top enters secondary extracting slurry tank by secondary fiber-film contact, fully contacts with alkali lye;
(3) alkali lye of discharging from secondary extracting slurry tank bottom recycles, the liquefied gas of discharging from secondary extracting slurry tank top enters three grades of extracting slurry tanks by three grades of fiber-film contacts, fully contact with alkali lye or water, from the liquefied gas purification that is of three grades of extracting slurry tank tops discharges.
3. method as claimed in claim 2, is characterized in that, in step (1), and the aqueous solution that described MDEA solvent is MDEA, mass concentration is 20 ~ 50%.
4. method as claimed in claim 2 or claim 3, is characterized in that, in step (2), described alkali lye is sodium hydroxide solution, and mass concentration is 10 ~ 30%.
CN201410077771.0A 2014-03-04 2014-03-04 A kind of device and method of oil refinery liquefied gas desulfuration purification CN103805274B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105477988A (en) * 2014-09-18 2016-04-13 山东鲁深发化工有限公司 Novel sulfur reduction process device
CN107227173A (en) * 2016-03-25 2017-10-03 中国石油化工股份有限公司 The combination unit of catalytic liquefaction gas deep desulfuration

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1785480A (en) * 2005-11-17 2006-06-14 江苏工业学院 Membrane adsorption natural gas desulfur method
CN101319150A (en) * 2007-06-07 2008-12-10 中国石油化工股份有限公司 Hot-soda washing desulfurization method
CN102408913A (en) * 2010-09-26 2012-04-11 刘宽 Light hydrocarbon sweetening process utilizing alkali liquor by stages
CN202446974U (en) * 2012-01-12 2012-09-26 宁波中一石化科技有限公司 Combination system for removing mercaptan from liquefied gas
CN103773498A (en) * 2013-11-28 2014-05-07 山东海成石化工程设计有限公司 High-temperature hydrogenation and purification process for liquefied gas materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1785480A (en) * 2005-11-17 2006-06-14 江苏工业学院 Membrane adsorption natural gas desulfur method
CN101319150A (en) * 2007-06-07 2008-12-10 中国石油化工股份有限公司 Hot-soda washing desulfurization method
CN102408913A (en) * 2010-09-26 2012-04-11 刘宽 Light hydrocarbon sweetening process utilizing alkali liquor by stages
CN202446974U (en) * 2012-01-12 2012-09-26 宁波中一石化科技有限公司 Combination system for removing mercaptan from liquefied gas
CN103773498A (en) * 2013-11-28 2014-05-07 山东海成石化工程设计有限公司 High-temperature hydrogenation and purification process for liquefied gas materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105477988A (en) * 2014-09-18 2016-04-13 山东鲁深发化工有限公司 Novel sulfur reduction process device
CN105477988B (en) * 2014-09-18 2018-03-23 山东鲁深发化工有限公司 New sulfur reduction process equipment
CN107227173A (en) * 2016-03-25 2017-10-03 中国石油化工股份有限公司 The combination unit of catalytic liquefaction gas deep desulfuration

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