CN107519746A - The processing method of sour gas in a kind of oil refinery dry gas recovery ethylene process - Google Patents

The processing method of sour gas in a kind of oil refinery dry gas recovery ethylene process Download PDF

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Publication number
CN107519746A
CN107519746A CN201610440780.0A CN201610440780A CN107519746A CN 107519746 A CN107519746 A CN 107519746A CN 201610440780 A CN201610440780 A CN 201610440780A CN 107519746 A CN107519746 A CN 107519746A
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CN
China
Prior art keywords
absorbent
amine
gas
dry gas
mdea
Prior art date
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CN201610440780.0A
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Chinese (zh)
Inventor
毛松柏
朱道平
杨绪甲
周志斌
余勇
陈园园
宋丽
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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Application filed by China Petroleum and Chemical Corp, Research Institute of Nanjing Chemical Industry Group Co Ltd filed Critical China Petroleum and Chemical Corp
Priority to CN201610440780.0A priority Critical patent/CN107519746A/en
Publication of CN107519746A publication Critical patent/CN107519746A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4516—Gas separation or purification devices adapted for specific applications for fuel vapour recovery systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention belongs to gas purification technique field, is related to a kind of processing method that sour gas in ethylene process is reclaimed from oil refinery dry gas.The present invention is proposed using a kind of amine with special construction with the MDEA aqueous solution as absorbent, and the amine of the special construction is a kind of monoethanolamine, and the wherein nitrogen-atoms of amido is located among six-membered cyclic compound.Using this absorbent while hydrogen sulfide is removed, NaOH removings CO compared with conventional art, can be saved with deeply removing carbon dioxide2Process, simple flow, disposal of pollutants is reduced, and reduce system energy consumption.

Description

The processing method of sour gas in a kind of oil refinery dry gas recovery ethylene process
Technical field
The invention belongs to gas purification technique field, is related to a kind of processing method that sour gas in ethylene process is reclaimed from oil refinery dry gas.
Background technology
Secondary operation of the oil refinery dry gas essentially from crude oil, such as catalytic cracking, thermal cracking and delayed coking, contain hydrogen, nitrogen, methane, ethene, ethane etc. in dry gas, before no suitably separation and recovery and comprehensive utilization technique, dry gas by as fuel gas or torch of setting fire burn-up, causes the wasting of resources and environmental pollution mostly.Therefore, the ethene and lighter hydrocarbons in dry gas are reclaimed, it has also become Integrated Refinery And Petrochemical realizes optimizing network resource utilization and reduces the important means of production cost of ethylene.
Ethene is reclaimed from dry gas to be refined to dry gas, wherein an important step is removing H2S and CO2。
Domestic earliest method is the technology that Lanzhou Petrochemical uses S＆W companies, i.e.,：Dry gas after conventional MDEA methods desulfurization removes CO in concentration dry gas after pressure-changed adsorption concentrating, then with MEA absorption process2And H2The sour gas such as S.
It is presently the most common from dry gas reclaim ethene method be：Dry gas after conventional MDEA methods desulfurization uses two sections of pressure swing adsorption techniques, removes the weakly adsorbed components such as most of hydrogen, methane, nitrogen, carbon monoxide, obtains half product gas rich in components such as ethene, ethane, then remove H through MDEA2S, NaOH removes CO2, dearsenification, deoxidation, denitrogenation, the processing of the purification such as drying, it is final to obtain the ethylene-rich product gas for meeting ethylene unit requirement.In order to reduce investment outlay, the energy consumption of device is reduced, the poor MDEA solution needed for dry gas desulfurization and ethylene-rich desulfurization is provided by a concentration regenerator.Yanshan Petrochemical, Maoming Petrochemical etc. obtain good economic benefit after using the technology.
It is another ethene is reclaimed from dry gas method be：Dry gas after conventional MDEA methods desulfurization is handled using Formula type decarbonization solvent again, removes most CO2。
But there is technological process length, have the defects of spent lye generation in these technologies.
The content of the invention
The present invention uses a kind of new Formula type MDEA solution, can be with deeply removing carbon dioxide while hydrogen sulfide is removed.
Alkyl alcoholamine is that CO is removed from gas2And H2S main method, wherein, alkanolamine solution and H2S reaction is reacted by the moment proton transfer of gas-film controlled, but and CO2Reaction mechanism it is then more complicated.Chemically from the point of view of viewpoint, the tertiary amine such as MDEA contains a tertiary N atom as active group, and this just means that this solution absorbs CO2Bicarbonate is only generated, therefore thermal regeneration can be carried out, its steam consumption is more than primary, secondary amine and CO2The rather stable carbaminate of generation carries out low during thermal regeneration.Therefore, the tertiary amine such as MDEA is widely used in various removing CO2During.
The tertiary amines such as MDEA and CO2Reaction path is as follows：
Reaction is controlled by (1), and reaction (1) is CO2Hydration reaction, the rate constant K at 25 DEG C OH =1041/mo1.s, [OH]=10-3~10-5mol.So reaction (3) is very slow reaction.
When adding a small amount of activator R in ertiary amine solution,During NH, CO is absorbed2Process can be explained with shuttle mechanism：Activator absorbs CO in table liquid film face2, then deliver CO to liquid phase2, and activator is reproduced, and continues to absorb the CO for diffusing through and2, such activator turns into CO2Carrier, inherently accelerate CO2Mass transfer velocity.Absorb CO2Reaction is carried out by following course.
It is related to two crucial parameters in this course of reaction：CO2With the reaction rate constant k of hydramine1With the stability constant k of carbaminate2.Research has shown that the size of the alkyl group near neighbouring amino nitrogen atom influences whether the k of hydramine1And k2.A certain size group can reduce the stability of carbaminate, but excessively huge group can reduce CO again2With the reaction rate of hydramine.Therefore, selection has the primary of appropriate steric effect（It is secondary）Amine absorbs CO as MDEA2Activator, do not generate stable carbaminate in absorption process, can avoid due to the problems such as regeneration energy consumption caused by carbaminate is larger, absorptive capacity is low and burn into is degraded.
The amine with special construction that the present invention uses for：The nitrogen-atoms of a kind of monoethanolamine, wherein amido is located among six-membered cyclic compound.
When amine used in the present invention with special construction is used in mixed way with MDEA, suitable use ratio is：Amine with special construction：MDEA=1：1.2~6.5（Mol ratio）, preferably 1：2~5.
In mixing amine aqueous solution used in the present invention, suitable total amine concentration is：20~70%（wt）, but preferably 30~50%（wt）.
In mixing amine aqueous solution used in the present invention, the additive such as corrosion inhibitor, defoamer and similar components can also be included, the concentration range of these additives is 0.01%~5%（wt）.
H in dry gas2S and CO2By being contacted with the mixing amine aqueous solution of the present invention to be removed.Make used absorbent regeneration simultaneously, remove absorbed H2S and CO2, then it is recycled to absorption step.Any known equipment in this area may be used to absorb, regenerate and other steps.
The present invention can save NaOH removings CO compared with conventional art2Process, simple flow, disposal of pollutants is reduced, and reduce system energy consumption.
Embodiment
The present invention is described in detail in reference to embodiment.
Embodiment：Below by example, the present invention will be described, and all solvents with the addition of appropriate corrosion inhibitor, defoamer and antisludging agent, but the present invention is not limited to these examples.
Comparative example 1
Certain oil refining apparatus catalysis drying gas 32t/h, pressure 1.1MPa, wherein, H2S~0.8%（vt）And CO2~3.2%（vt）, solvent is formulated as absorbent after an absorption tower processing using certain MDEA, the H in gas2The μ L.L of S~5-1, CO2~52 μ L.L-1。
Embodiment 1
Certain oil refining apparatus catalysis drying gas 32t/h, pressure 1.1MPa, wherein, H2S~0.8%（vt）And CO2~3.2%（vt）, using the amine liquid of the present invention（MDEA2.0mol/l, cyclic amine 0.4mol/l）After being handled by an absorption tower, the H in gas2S≤5μL.L-1, CO2≤50μL.L-1。
Comparative example 2
Certain company has built a set of 2 × 104Nm3/ h dry gas concentration units, H in concentrate gas2S~0.04%（vt）、CO2~2.8%（vt）, solvent is formulated as absorbent using certain MDEA, amine liquid internal circulating load is 33t/h, after amine is washed, H in concentrate gas2The μ L.L of S~5-1、CO2~800 μ L.L-1。
Embodiment 2
Absorbing liquid in comparative example is changed to the absorbing liquid of the present invention（MDEA2.3mol/l, cyclic amine 0.3mol/l）Afterwards, the internal circulating load of solution drops to 9 t/h, significantly reduces the regenerated load of amine liquid, has significant energy-saving effect；Amine washes H in rear concentrate gas2S≤5μL.L-1、CO2≤50μL.L-1., caustic wash process is eliminated, while mitigate the alkali consumption of ethylene unit caustic wash process, reduce the discharge capacity of salkali waste.

Claims (7)

  1. A kind of 1. processing method of sour gas in oil refinery dry gas recovery ethylene process, it is characterized in that it is used in mixed way using a kind of amine with special construction with MDEA, absorbent as sour gas, the amine of described special construction is a kind of monoethanolamine, wherein the nitrogen-atoms of amido is located among six-membered cyclic compound, and the amine of the special construction and MDEA mol ratio are：1：1.2~6.5.
  2. 2. the method as described in claim 1, it is characterized in that the amine of the special construction and MDEA mol ratio are：1：2~5.
  3. 3. the method as described in claim 1, the mass percent concentration of the absorbent are：20~70%.
  4. 4. method as claimed in claim 3, the mass percent concentration of the absorbent are：30~50%.
  5. 5. the method as described in claim 1, it is characterized in that including additive in used absorbent, the additive includes corrosion inhibitor, defoamer.
  6. 6. method as claimed in claim 5, it is characterized in that the concentration range of additive is 0.01%~5%（wt）.
  7. 7. the method as described in claim 1, it is characterized in that the acid gas in dry gas, by being contacted with absorbent to be removed, used absorbent is regenerated by removing absorbed acid gas, absorbent regeneration Posterior circle to absorption step.
CN201610440780.0A 2016-06-20 2016-06-20 The processing method of sour gas in a kind of oil refinery dry gas recovery ethylene process Pending CN107519746A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1835786A (en) * 2003-06-12 2006-09-20 坎索尔夫科技公司 Method for recovery of CO2 from gas streams
CN101537340A (en) * 2009-04-30 2009-09-23 西安热工研究院有限公司 Smoke CO*absorbent
CN102343204A (en) * 2010-08-04 2012-02-08 中国石油化工集团公司 Method for removing sulfides from acidic gas flow
CN105664672A (en) * 2016-04-05 2016-06-15 江苏大海能源科技有限公司 Compound liquid decarbonizing agent for removing high-concentration CO2 in gas
CN105664698A (en) * 2016-04-05 2016-06-15 江苏大海能源科技有限公司 Compound liquid desulfurizing agent and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1835786A (en) * 2003-06-12 2006-09-20 坎索尔夫科技公司 Method for recovery of CO2 from gas streams
CN101537340A (en) * 2009-04-30 2009-09-23 西安热工研究院有限公司 Smoke CO*absorbent
CN102343204A (en) * 2010-08-04 2012-02-08 中国石油化工集团公司 Method for removing sulfides from acidic gas flow
CN105664672A (en) * 2016-04-05 2016-06-15 江苏大海能源科技有限公司 Compound liquid decarbonizing agent for removing high-concentration CO2 in gas
CN105664698A (en) * 2016-04-05 2016-06-15 江苏大海能源科技有限公司 Compound liquid desulfurizing agent and application thereof

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Application publication date: 20171229

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