CN104193034A - Amine liquid purification treatment system - Google Patents
Amine liquid purification treatment system Download PDFInfo
- Publication number
- CN104193034A CN104193034A CN201410461234.6A CN201410461234A CN104193034A CN 104193034 A CN104193034 A CN 104193034A CN 201410461234 A CN201410461234 A CN 201410461234A CN 104193034 A CN104193034 A CN 104193034A
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- tank
- removes
- amine
- metallic cation
- thermo
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- 150000001412 amines Chemical class 0.000 title claims abstract description 61
- 239000007788 liquid Substances 0.000 title claims abstract description 52
- 238000000746 purification Methods 0.000 title claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- 239000012530 fluid Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001457 metallic cations Chemical class 0.000 claims description 42
- 150000002500 ions Chemical class 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000011033 desalting Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical compound C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000035508 accumulation Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- -1 highlights Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Gas Separation By Absorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to an amine liquid purification treatment system, which comprises a suspended matter removal system, a thermal-stability salt negative ion removal system, a metallic positive ion removal system, a circulating fluid tank and a circulating fluid pump connected to the circulating fluid tank, wherein the suspended matter removal system, the thermal-stability salt negative ion removal system and the metallic positive ion removal system are sequentially connected through a pipeline; the circulating fluid tank is respectively connected to a desalting water supply pipeline and the circulating fluid pump through a pipeline and a valve; and the circulating fluid pump is respectively connected to a suspended matter removal tank in the suspended matter removal system, a thermal-stability salt negative ion removal tank in the thermal-stability salt negative ion removal system and a metallic positive ion removal tank in the metallic positive ion removal system through a pipeline and a valve. According to the system disclosed by the invention, processed amine liquid can reduce a metallic positive ion level in the amine liquid system to a normal level, thus being beneficial for stable operation of a desulfurization device.
Description
Technical field
The present invention relates to a kind of amine purification treatment system, the cleaning treatment system of the amine liquid particularly using in the sulfur removal technology of refinery and natural gas plant.
Background technology
In oil and gas processing gas purification process, adopting hydramine method desulfurization and decarburization is a kind of of paramount importance method, and wherein the selective adsorption technique of N methyldiethanol amine (MDEA) is current domestic most popular gas purifying technique.The major advantage of MDEA is less energy-consumption, low-corrosiveness and low degradation rate, and since coming out from the eighties in last century, development is very rapid.So far MDEA and formula solvent application nearly cover whole gas sweetening decarburization field.
Along with the requirement of environmental protection and energy saving aspect purification is further strict, also more and more higher to the specification of quality of the performance of gas-cleaning installation and amine liquid in recent years.In hydramine sweetening process, because feeding gas is brought into and the reasons such as oxidative degradation of amine, can bring a series of harm to device: corrosion of equipment, the foaming of amine liquid, frequently, amine liquid runs and damages seriously simultaneously for cleaning filter, replacing.At present typical amine purification treating processes has distillating recovering solvent, and adopts filtration, ion exchange method to remove the method for impurity in amine liquid.Wherein the method for filtration+ion-exchange is applied comparatively extensive greatly because of simple to operate, treatment capacity.But common amine purification method is considered the removal of suspended solid and thermal-stable salt, and ignored the removal of strong cation in amine liquid.
As patent of invention 200810057069.2, a kind of cleaning treatment system is disclosed, be only provided with the device of removing suspended solid and thermal-stable salt, do not remove cationic device.In amine liquid system, due to unstripped gas carries, equipment corrosion etc., can cause a large amount of accumulations of metallic cation in amine liquid.A large amount of existence of metallic cation can cause following problem: gas product is defective, and exhaust emissions exceeds standard; Amine absorption and analyzing efficiency are low, and in lean solution, acid gas residual quantity is large, and device processing power declines; Shape scaling salt block system pipeline.Especially using anionresin technology to remove after the thermo-stabilising salts negatively charged ion in amine liquid, the impact of metallic cation particularly highlights, and therefore, is also the problem can not be ignored to the removal of metallic cation.The present invention is the technological improvement development of carrying out on the basis of patent 200810057069.2.
Summary of the invention
The present invention is directed to the existing state of the art, a kind of amine purification system is provided, can remove thermo-stabilising salts negatively charged ion and metallic cation in amine liquid simultaneously, make amine purification.The method can apply to the system of the problem that causes because of metallic cation too high levels in the devices such as hydramine method desulfurization.
Above object of the present invention is achieved by the following technical solution:
An amine purification treatment system, comprises the recycle liquid pump that removes suspended substance (SSX) system, removes thermo-stabilising salts negatively charged ion (HSSX) system, removes metallic cation (SCX) system and circulation fluid case and be attached thereto.Remove suspended substance system, remove thermo-stabilising salts negatively charged ion system and remove between metallic cation system and connect successively by pipeline, described circulation fluid case is connected with de-mineralized water supply line and recycle liquid pump from user respectively with valve by pipeline, and described recycle liquid pump is connected with the metallic cation tank that removes removing in metallic cation system with the thermo-stabilising salts negatively charged ion tank that removes that removes suspended substance tank, removes in thermo-stabilising salts negatively charged ion system removing in suspended substance system respectively with valve by pipeline.
In this purification system, comprise the metallic cation system that removes, and remove after metallic cation system is placed in and removes thermo-stabilising salts negatively charged ion system, remove in metallic cation (SCX) system and adopt resin cation (R.C.), the resin cation (R.C.) after saturated adopts the acid solution that mass concentration is 3% to regenerate.Amine liquid, after the system of entering, first removes suspended substance and thermo-stabilising salts negatively charged ion, then enters SCX system and remove the metallic cation in amine liquid by Zeo-karb.
Advantage of the present invention is as follows:
1. the amine liquid after processing by SCX system, can be reduced to normal level by the metallic cation level in amine liquid system, is conducive to the steady running of desulfurizer.
2. will remove metallic cation (SCX) system and be placed in and remove after thermo-stabilising salts negatively charged ion (HSSX) system canister, and can reduce Zeo-karb to the cationic absorption of amine.
3. the anionresin after saturated is regenerated with alkaline solution, Zeo-karb after saturated is regenerated with acid solution, two kinds of regenerative wastewater are mixed the pH value that can reduce waste water, make it enter more easily processing after Waste Water Treatment, can not affect the normal operation of waste water system.
Accompanying drawing explanation
Fig. 1 is amine purification system schema of the present invention.
Embodiment
As shown in Figure 1, be system architecture signal of the present invention and schema.Comprise the recycle liquid pump 5 that removes suspended substance (SSX) tank 1, removes thermo-stabilising salts negatively charged ion (HSSX) tank 2, removes metallic cation (SCX) tank 3 and circulation fluid case 4 and be attached thereto.Remove suspended substance tank 1, remove thermo-stabilising salts negatively charged ion tank 2 and remove between metallic cation tank 3 and connect successively by pipeline, circulation fluid case 4 is connected with de-mineralized water supply line and recycle liquid pump 5 from user respectively with valve by pipeline, recycle liquid pump 5 by pipeline and valve respectively with remove suspended substance tank 1, remove thermo-stabilising salts negatively charged ion tank 2 and remove metallic cation tank 3 and be connected.
In this purification system, comprise and remove metallic cation tank 3, and remove after metallic cation tank 3 is placed in and removes thermo-stabilising salts negatively charged ion tank 2, remove in metallic cation (SCX) tank 3 and adopt resin cation (R.C.), the resin cation (R.C.) after saturated adopts the acid solution that mass concentration is 3% to regenerate.
Purification process: the amine liquid not purifying is introduced into and removes suspended substance (SSX) tank 1 to remove the solid impurity in amine liquid, the amine liquid of removing suspended substance enters and removes thermo-stabilising salts negatively charged ion (HSSX) tank 2 removal thermo-stabilising salts negatively charged ion, enter subsequently and remove the metallic cation that metallic cation (SCX) tank 3 is removed in amine liquid, the purification amine liquid removing after positively charged ion returns to amine system.
When system is after operation for some time, the suspended substance that SSX tank is held back is more and more, thereby has reduced its processing power.When SSX tank filtration yield reaches its set(ting)value or inlet outlet pressure differential and reaches set(ting)value, need to clean SSX tank, to recover its operating flux.
1) row's amine is just washed
Circulation fluid enters SSX tank from SSX tank top forward, and adjust flux is set(ting)value, and the purification amine in SSX tank is pressed into user's amine pipeline.Circulation flushing SSX tank, rinses water outlet and changes and enter in cyclic water tank, to reduce the loss of amine.
2) backwash
De-mineralized water adverse current enters SSX tank, and adjust flux is set(ting)value.When water inlet volume reaches set(ting)value, SSX tank cleans and finishes, and can enter amine and start new circulation.
After HSSX tank and SCX tank operation certain hour, when the two one of the exchange capacity amine liquid exchange capacity differential pressure that reaches setting while being greater than set(ting)value, need to carry out manipulation of regeneration to it, make it again possess the sub-ability of disengaging.
1) row's amine is just washed
Circulation fluid forward enters HSSX tank and SCX tank, utilizes the solution in circulation fluid case 4 to carry out wash cycles, reduces the loss of amine.
2) regeneration
Regulating the flow of de-mineralized water is set(ting)value, quantitative with calculated amount pump, HSSX tank oppositely pumps into the sodium hydroxide solution regeneration of 4% (quality), SCX tank oppositely pumps into the hydrochloric acid soln of 3% (quality) and regenerates, and regenerated liquid adverse current enters in tank, so that resin can become flexible and again arrange, regenerated liquid is uniformly distributed, improve regeneration effect, when acid, alkali consumption reach set(ting)value, regeneration ending.
3) displacement
After regeneration ending, stop into acid, alkali lye, continue adverse current and enter de-mineralized water, adjusting flooding velocity is set(ting)value, carries out replacement operator.By displacement, can discharge remaining in resin middle acid, alkali lye.When going out water power dodar after set(ting)value, replacement completion.
In regeneration and replacement process, alkali pump first starts afterwards and stops than sour pump, and keeping regeneration water outlet to mix rear is alkalescence.
4) just wash
Circulation fluid forward enters HSSX tank and SCX tank, is then back to circulation fluid case.Adjust flux is set(ting)value, after moving to set(ting)value, is just washing end.
5) enter amine setting-out
Amine liquid forward enters HSSX tank and SCX tank, and the replacing water in HSSX tank is pressed into circulation fluid case, when entering amine volume to set(ting)value, stops setting-out, starts new circulation.
Embodiment:
In tower, I oil gas treatment station belongs to first oil gas treatment station of I gas field development trial plot in Tarim Oilfield tower.There are two large feature: a in handled Sweet natural gas ore deposit, this station, belong to Condensate Field; B, gas mineral water saltiness are very high.Go into operation the initial stage in this station in October, 2010, a large amount of condensate oils enter amine liquid with unstripped gas, cause amine liquid to pollute, amine liquid is muddy, band oil obviously, foaming is serious, cause the foaming of flash distillation gas carrying liquid, absorption tower to block that liquid, liquid phase circulation are smooth, the problems such as liquid are blocked in regenerator column foaming, when serious, even occurred that primary system stops, and had affected steady running and the sweetening effectiveness of desulphurization system.
This situation needs amine refining plant except there being thermo-stabilising salts and filtration unit in the amine of removal liquid, also must have cationic device in the amine of processing liquid simultaneously, otherwise is difficult to reach the purification target of expection, even can have influence on the steady running of amine purification system.
In order to address the above problem, removing suspended substance (SSX) system and removing on the basis of thermo-stabilising salts negatively charged ion (HSSX) system, increased metallic cation (SCX) system that removes, in December, the 2010 I oil gas treatment station in tower of being installed on of the present invention formally comes into operation.Come into operation latter five days, amine liquid foamed phenomenon is effectively controlled, and desulphurization system amine liquid turbid phenomenon is improved.The operating performance of apparatus of the present invention refers to table 1, is the steady salt of heat in device portal and exit amine liquid, positively charged ion and the contrast of negatively charged ion test data.Anion and cation exchange resin unit on this covering device has played good decontamination effect improving equally, has effectively slowed down equipment corrosion, has prevented tower, device equipment salification phenomenon that the accumulation of salinity in amine liquid causes.
Table 1
Amine liquid, after the system of entering, first removes suspended substance and thermo-stabilising salts negatively charged ion, then enters and remove metallic cation system and remove the metallic cation in amine liquid by Zeo-karb.Owing to adding the metallic cation system that removes, can remove the metallic cation in amine liquid system, effectively slowed down equipment corrosion, prevented tower, device equipment salification phenomenon that the accumulation of salinity in amine liquid causes, guarantee the steady running of desulfurizer.
Claims (3)
1. an amine purification treatment system, is characterized in that: comprise the recycle liquid pump that removes suspended substance system, removes thermo-stabilising salts negatively charged ion system, removes metallic cation system and circulation fluid case and be attached thereto; The described suspended substance system that removes, remove thermo-stabilising salts negatively charged ion system and remove between metallic cation system and connect successively by pipeline, described circulation fluid case is connected with de-mineralized water supply line and recycle liquid pump respectively with valve by pipeline, and described recycle liquid pump is connected with the metallic cation tank that removes removing in metallic cation system with the thermo-stabilising salts negatively charged ion tank that removes that removes suspended substance tank, removes in thermo-stabilising salts negatively charged ion system removing in suspended substance system respectively with valve by pipeline.
2. amine purification treatment system according to claim 1, is characterized in that: after the described metallic cation system that removes is placed in and removes thermo-stabilising salts negatively charged ion system, remove metallic cation system and adopt resin cation (R.C.).
3. amine purification treatment system according to claim 2, is characterized in that: the acid solution that the saturated rear employing mass concentration of described resin cation (R.C.) is 3% is regenerated.
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CN201410461234.6A CN104193034B (en) | 2014-09-11 | 2014-09-11 | A kind of amine purification processes system |
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CN201410461234.6A CN104193034B (en) | 2014-09-11 | 2014-09-11 | A kind of amine purification processes system |
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CN104193034A true CN104193034A (en) | 2014-12-10 |
CN104193034B CN104193034B (en) | 2016-06-08 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106178591A (en) * | 2015-05-08 | 2016-12-07 | 北京思践通科技发展有限公司 | A kind of method purifying organic amine |
CN107930399A (en) * | 2017-11-21 | 2018-04-20 | 攀钢集团攀枝花钢铁研究院有限公司 | The removal methods of foreign ion in a kind of organic amine desulfuration solution |
CN108392896A (en) * | 2018-05-07 | 2018-08-14 | 山东胜星化工有限公司 | A kind of amine liquid removes the control system of coke powder purifier |
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CN101219815A (en) * | 2008-01-29 | 2008-07-16 | 王建军 | Cleaning treatment system |
AU2008202311A1 (en) * | 2008-05-22 | 2009-12-10 | Al-Samadi, Riad Dr | High Water Recovery Single Stage Membrane Process |
CN103979716A (en) * | 2014-05-22 | 2014-08-13 | 西安热工研究院有限公司 | System and method for purifying and recycling amine liquid of smoke CO2 trapping system for coal-fired power plant |
CN204058129U (en) * | 2014-09-11 | 2014-12-31 | 王建军 | A kind of amine purification treatment system |
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2014
- 2014-09-11 CN CN201410461234.6A patent/CN104193034B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101219815A (en) * | 2008-01-29 | 2008-07-16 | 王建军 | Cleaning treatment system |
AU2008202311A1 (en) * | 2008-05-22 | 2009-12-10 | Al-Samadi, Riad Dr | High Water Recovery Single Stage Membrane Process |
CN103979716A (en) * | 2014-05-22 | 2014-08-13 | 西安热工研究院有限公司 | System and method for purifying and recycling amine liquid of smoke CO2 trapping system for coal-fired power plant |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106178591A (en) * | 2015-05-08 | 2016-12-07 | 北京思践通科技发展有限公司 | A kind of method purifying organic amine |
CN106178591B (en) * | 2015-05-08 | 2019-03-15 | 北京思践通科技发展有限公司 | A method of purification organic amine |
CN107930399A (en) * | 2017-11-21 | 2018-04-20 | 攀钢集团攀枝花钢铁研究院有限公司 | The removal methods of foreign ion in a kind of organic amine desulfuration solution |
CN108392896A (en) * | 2018-05-07 | 2018-08-14 | 山东胜星化工有限公司 | A kind of amine liquid removes the control system of coke powder purifier |
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