CN100333823C - Method for purifying deterioration amine liquid using highly basic anion exchange resin - Google Patents
Method for purifying deterioration amine liquid using highly basic anion exchange resin Download PDFInfo
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- CN100333823C CN100333823C CNB2004100534700A CN200410053470A CN100333823C CN 100333823 C CN100333823 C CN 100333823C CN B2004100534700 A CNB2004100534700 A CN B2004100534700A CN 200410053470 A CN200410053470 A CN 200410053470A CN 100333823 C CN100333823 C CN 100333823C
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- amine
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- 150000001412 amines Chemical class 0.000 title claims abstract description 129
- 239000007788 liquid Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000006866 deterioration Effects 0.000 title claims abstract description 36
- 239000003957 anion exchange resin Substances 0.000 title claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 110
- 229920005989 resin Polymers 0.000 claims abstract description 110
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 58
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- 230000008929 regeneration Effects 0.000 claims abstract description 36
- 238000011069 regeneration method Methods 0.000 claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 35
- 238000000746 purification Methods 0.000 claims abstract description 20
- -1 alcohol amine Chemical class 0.000 claims abstract description 17
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 71
- 239000002585 base Substances 0.000 claims description 24
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 19
- 229960002668 sodium chloride Drugs 0.000 claims description 16
- 230000004087 circulation Effects 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 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 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical group C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043237 diethanolamine Drugs 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 30
- 239000004925 Acrylic resin Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 238000011010 flushing procedure Methods 0.000 description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000097 high energy electron diffraction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The present invention discloses a method for purifying deterioration amine liquid by highly basic anion exchange resin, which uses heat steady-state salt in deterioration alcohol amine solution in desulfurizing devices, etc. according to an amine eliminating method by the highly basic anion exchange resin, and the method for purifying deterioration amine liquid by highly basic anion exchange resin carries out the regeneration of the resin by the use of a sodium hydroxide one-step method and the periodic use of a sodium chloride anabiotic technology. The adopted highly basic anion exchange resin can be 1 type phenylethylene-divinylbenzene framework highly basic anion exchange resin, 2 type phenylethylene-divinylbenzene framework highly basic anion exchange resin and acrylic acid framework highly basic anion exchange resin. The method for purifying deterioration amine liquid by highly basic anion exchange resin has the advantages that the resin has the strong capability of eliminating and absorbing sulfur hydrogen acid radicals, and the resin can be used for eliminating the heat steady-state salt in the amine liquid in a long period; the technology of the resin regeneration is easy, the purification efficiency of the amine liquid is high, and the exchange capacity of the resin can be kept to about 77%.
Description
Technical field
The present invention relates to the ion-exchange purification techniques, is the method that a kind of spent ion exchange resin is removed the impurity such as heat stable salts in the deterioration amine liquid specifically.
Background technology
Natural gas plant and oil plant are usually with the H in the hydramine absorption plant removal air-flow (natural gas, dry gas, liquefied gas and the petroleum gas that comes self-catalysis, cracking, coking etc. to install)
2S and CO
2Sour gas, absorbent mainly are 20%~50% aqueous alkanolamines." the amine liquid " of indication of the present invention is general name, various alkanolamines (one or more) aqueous solution that is considered when comprising desulfurization and adopts, as: MEA (MEA), diethanol amine (DEA), triethanolamine (TEA), diglycolamine (DGA), diisopropanolamine (DIPA) and methyl diethanolamine (MDEA).
The technical process of acid gas removal body is to make air communication cross the amine absorption tower, with poor amine liquid counter current contacting, CO
2And H
2The S sour gas is dissolved in the amine liquid, and to form soluble pure amine salt (be protonated hydramine cation and HS-and HCO
3-In conjunction with).Then, water, unreacted hydramine and pure amine salt solution enter stripper, and this class hydramine salinity is separated and discharged H
2S and CO
2, amine liquid circulates once more and enters absorption tower and stripper.But, remove H in the air-flow
2S and CO
2Also comprise SO outward,
2, CS
2, sour gas such as HCN and COS, these gases carry out and the reaction of amine liquid, form alkanolamine equally.And these salt can not be removed by stripper, are trapped in the system and constantly accumulation.
Another problem is, if oxygen enters the alkanolamine system, sour gas and hydramine oxidation form other pure amine salt, and modal is thiosulfuric acid (S
2O
3 2-) salt, sulfuric acid (SO
4 2-) salt, thiocyanic acid (SCN
-) salt, polythionate, acetate, formates, nitrate and chlorine (Cl
-) salt etc., these salt can not be regenerated by stripper.
Can not be referred to as heat stable salts (Heat Stable Salts is called for short HSS) by the pure amine salt of heat regeneration, it brings following harm to device: one of major reason of equipment heavy corrosion; Salt and corrosion product cause the obstruction of device; The heat stable salts anion combines with amine and forms constraint amine, has reduced effective amine concentration of amine liquid, makes the desulfuration efficiency of amine liquid descend; The heat stable salts of high-load also makes the foaming trend aggravation of amine liquid, further reduces the device desulfuration efficiency and makes the amine liquid of device run the consumption increase.Thereby need it is handled.
How to solve the heat stable salts problem in the amine liquid, domestic still do not have processing method preferably at present, mainly is that amine liquid is emitted or disposes, and normally regularly emits a part of amine.Because the COD content higher (6% amine liquid COD mass concentration reaches 30, more than the 000mg/L) of amine liquid is bigger to the sewage disposal system impact if enter sewage, and environment and human body are constituted harm.Another kind method is that dirty amine liquid is introduced delayed coking unit, carry out pyrolytic and handle (with reference to " petroleum refining and chemical industry " the 34th volume the 1st phase " delayed coking unit processing disused aine liquid "), but this technology causes problems such as corrosion of heating furnace water injection pipe and the obstruction of coking fractional distillation column tower tray easily.
Similar techniques is disclosed Chinese patent CN1 on October 6th, 1999,230, and the disclosed a kind of method of 545A with anion exchange resin regeneration inferior sulfolane.This method is earlier through distillation, again by macroreticular weakly base styrene anion exchange resin layer, to remove acidic materials wherein with inferior sulfolane.
Purify amine liquid and be to use the way of distillation the earliest.The way of distillation can be applied to the MEA system, but can not in diethanol amine (DEA), triethanolamine (TEA) and methyl diethanolamine systems such as (MDEA), use, because the boiling point of these alkanolamines is very high (under the 760mmHg,>400F), oxidation and degraded take place in hydramine easily under so high temperature.And prevent that the amine thermal degradation from must use decompression distillation, but that decompression distillation purifies the equipment and the operating cost of amine liquid is too high, so the way of distillation never is applied to remove the heat stable salts in the amine liquid.
Spent ion exchange resin is removed the method for the heat stable salts in the amine liquid and is compared with other amine liquid purification methods, has low, the simple characteristics of expense.But owing to not only contain heat stable salts in the deterioration amine liquid but also contain the hydramine degradable component of chemical composition complexity, as " HEED ", " BHEEU " etc. contains organic impurities in addition in the amine liquid, pollute resin easily, increased difficulty for ion-exchange purification amine liquid.Water treatment facilities uses ion exchange technique very successful, but the anion total concentration in the water is much lower, and the ion that has strong affinity with resin still less, so the regeneration of ion-exchange resin ratio is easier to, and is also lower to the requirement of resin.On the contrary, the anion concentration of amine treatment system is very high, needs frequent regeneration to remove these anion.In addition, the anion stronger with resin affinity is as sulfur hydrogen anion, formate, acetate etc., because of being difficult to desorption from the cation adsorption group of resin.So use ion-exchange purification regeneration deterioration amine liquid, most critical be to select the type of resin and the technology of resin regeneration for use.
In U.S. Patent No. 5, in 162,084, use sulfuric acid and NaOH regenerating resin, I type styrene-divinylbenzene skeleton strong-base anion-exchange resin is selected in special recommendation for use, because I type resin exchange capacity is than II type styrene-divinylbenzene skeleton strong-base anion-exchange resin height.
In U.S. Patent No. 5,788, in 864, adopt the regeneration of NaOH one-step method, it selects highly basic II type styrene-divinylbenzene skeleton strong-base anion-exchange resin for use, and the exchange capacity of regeneration back resin can return to original about 50%.
Summary of the invention
Technical problem to be solved by this invention is that a kind of method that purifies deterioration amine liquid with strong-base anion-exchange resin is provided at the prior art present situation, this method can apply to the purified treatment of deterioration amine liquid in the device such as amine method desulfurization and the regeneration of exchanger resin, to remove impurity such as heat stable salts anion in the amine liquid and amine liquid is used for recirculation, guarantee that amine aqueous solution moves under low heat stable salts content.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this kind purifies the method for deterioration amine liquid with strong-base anion-exchange resin, it is characterized in that may further comprise the steps:
A, absorption: with temperature is that 30~60 ℃ and the deterioration amine liquid handled are after filtration flowed through and are filled with the resin bed of strong-base anion-exchange resin, and the heat stable salts anion in the resin adsorption deterioration amine liquid is purified deterioration amine liquid; When purifying amine liquid because of the employing suction type, the anion load in the resin bed constantly increases, so need remove the anion that adsorbs in the resin bed by following step b;
B, regeneration: after treating that resin adsorption in the described resin bed is saturated, wash described resin bed, make the resin in the described resin bed obtain regeneration and recover adsorption capacity substantially with alkali metal hydroxide aqueous solution;
C, repetition above-mentioned steps a and step b;
D, recovery: whenever carry out above-mentioned steps a and step b the circulation 50~200 times after, wash described resin bed with sodium-chloride water solution, remove the organic matter and the stronger SCN of affinity that are adsorbed on the resin
-, to keep the ion exchange capacity of resin; It should be noted that and then can reduce amine liquid purification efficiency, and the concentration of chlorion in the amine liquid is increased, so the present invention adopts the method that regularly makes the resin recovery with the sodium-chloride water solution flushing if sodium-chloride water solution is used in resin regeneration at every turn.
Described strong-base anion-exchange resin can be selected I type styrene-divinylbenzene skeleton strong-base anion-exchange resin (hereinafter to be referred as I type styrene resin), II type styrene-divinylbenzene skeleton strong-base anion-exchange resin (hereinafter to be referred as II type styrene resin) or acrylic backbone strong-base anion-exchange resin (hereinafter to be referred as acrylic resin) for use.
Filtration in the described adsorption step comprises multistage filtering, wherein should comprise with active carbon filter at least and filtering.
Whether the method that the present invention purifies deterioration amine liquid also comprises the heat stable salts analysis on Content in the gained amine liquid after described adsorption treatment, to determine the time that the ion exchange resin adion reaches capacity and to need the resin processing of regenerating.
If the single resin bed of purification of deterioration amine liquid of the present invention, technology is step, because need stop into amine liquid when ion exchange resin regeneration.If use plural a plurality of resin bed parallel connection, handover operation between the resin bed in parallel then can be realized carrying out continuously of deterioration amine liquid purification.
Described alkali metal hydroxide aqueous solution preferably concentration is the sodium hydrate aqueous solution of 10~20wt%.
The concentration of described sodium-chloride water solution is preferably 1~20wt%.
Described deterioration amine liquid refers to that the content of heat stable salts wherein is the aqueous solution of one or more hydramine of 1~15%, and hydramine comprises MEA, diethanol amine, triethanolamine, diglycolamine, diisopropanolamine (DIPA) and methyl diethanolamine etc.
Described heat stable salts anion comprises organic acid, sour gas and inorganic acid radical.Described organic acid comprises HCOO
-, CH
3COO
-And oxalate etc.; Described inorganic acid radical comprises SCN
-, Cl
-, S
2O
3 2-, SO
4 2-And NO
3 -Deng; Described sour gas comprises SO
2, CS
2, HCN, COS and polythionic acid etc.
Therefore, the inventive method can be summarized as: purify deterioration amine liquid with strong-base anion-exchange resin, the heat stable salts anion in the amine liquid is removed in absorption, make amine liquid be used for recirculation, regeneration of resin then adopts the regeneration of NaOH one-step method and regularly uses the technology of sodium chloride solution recovery.The effect of using sodium chloride solution to recover regularly is to improve the exchange capacity after resin is repeatedly regenerated for a long time.
Utilization the inventive method has following effect:
1. greatly reduce equipment corrosion, prolong the service life of amine treating apparatus, reduce the maintenance and operation expense of equipment.
2. reduce the amine liquid loss of amine treating apparatus, reduced the operating cost of device.
3. improved the desulfuration efficiency (, having increased the amine amount that can be used for handling gas) of desulfurizer, guaranteed the quality of gas treatment equipment product owing to discharge constraint amine.
The inventive method has the following advantages with respect to prior art:
1, adopt strong-base anion-exchange resin to purify amine liquid, the thiocyanate ion that affinity is stronger and other heat stable salts ions are wash-out from resin more easily, and this resin has the strong and not breakable advantage of good springiness of anti-organic matter pollution capacity.Wherein, especially be good with acrylic resin, because adopt acrylic resin to purify amine liquid, the thiocyanate ion that affinity is stronger and other heat stable salts ions are wash-out from resin more easily, and acrylic resin has the strong and not breakable advantage of good springiness of anti-organic matter pollution capacity, and its exchange capacity is also higher in addition.
2, the present invention selects strong-base anion-exchange resin especially for use, is applied to purify amine liquid, removes heat stable salts in the amine liquid.Strong-base anion-exchange resin has the good stronger SCN of desorption affinity
-Ability adopts the regeneration of NaOH one-step method, and the exchange capacity of resin can remain on about 65%.
3, the present invention's strong-base anion-exchange resin, continuously purifying heat stable salts content is the amine liquid of 1~15wt%, adopts the repeatedly regeneration for a long time of NaOH one-step method, the exchange capacity of resin can remain on 59%.
4, the present invention's strong-base anion-exchange resin, continuously purifying heat stable salts content is the amine liquid of 1~15wt%, adopt the regeneration of NaOH one-step method, regularly use sodium-chloride water solution flushing recovery again, resin still can remain on 77% through the long-term exchange capacity that uses.This regeneration technology can make resin keep purifying efficiently for a long time amine liquid.
Description of drawings
Fig. 1 is the amine liquid regeneration technology easy device flow chart of the embodiment of the invention of the single resin bed of employing;
The breakthrough curve of Fig. 2 II type styrene resin heat stable salts changes.When flowing through resin bed with amine liquid, the concentration of heat stable salts is represented with respect to amine liquid elution volume.Resin is at the breakthrough curve of 100 circulations and 2300 circulation times.
Fig. 3 II type styrene resin purifies amine liquid, a step method of reproduction experiment cycle-index and heat stable salts content (HSS%) variation relation figure.
Fig. 4 acrylic resin is with one-step method regeneration tests cycle-index and heat stable salts content (HSS%) variation relation figure.
The specific embodiment
Below in conjunction with accompanying drawing and example the present invention is described in further detail.
Example 1~3
In the glass column of three internal diameter 15mm, be respectively charged into the fresh I type of 30ml styrene resin (A), II type styrene resin (B) and acrylic resin (C).With 5~20% NaOH transition, resin is by Cl
-Type converts OH to
-Type.Each resin sample is carried out titration with standard hydrochloric acid, is the initial exchange capacity of resin.
Then, five regeneration cycle of every kind of resin experience: making the saturated solution of resin adsorption is the 30%MDEA/ aqueous solution, contain 0.5 milliequivalent KSCN in wherein every gram solution, the resin bed 15 minutes of flowing through is with the NaOH flushing resin regeneration in 60 minutes of 10~20wt%.After each regeneration, mixed with resin is even, measure the exchange capacity of various resins with the standard salt acidometric titration.The exchange capacity of each recycled resin is as shown in table 1.
Three kinds of different resins absorption of table 1 SCN
-After the regeneration, the exchange capacity change list:
Cycle-index | Example 1 | Example 2 | Example 3 | |||
I type styrene resin (A) | II type styrene resin (B) | Acrylic resin (C) | ||||
Exchange capacity eq/L | Percentage % with respect to the initial exchange capacity | Exchange capacity eq/L | Percentage % with respect to the initial exchange capacity | Exchange capacity eq/L | Percentage % with respect to the |
|
0 | 1.29 | 100 | 1.09 | 100 | 1.25 | 100 |
1 | 0.27 | 21 | 0.57 | 52 | 0.90 | 71 |
2 | 0.22 | 17 | 0.54 | 50 | 0.89 | 68 |
3 | 0.19 | 15 | 0.56 | 51 | 0.86 | 65 |
4 | 0.17 | 13 | 0.53 | 49 | 0.85 | 66 |
As can be seen from Table 1, to SCN
-The desorption ability acrylic resin best, I type styrene resin desorption ability is the poorest.
Example 4
The 200 milliliters of I type styrene resins (A) of packing in the glass column of internal diameter 20mm wash about 120 minutes transition with 500 milliliters of 5~20wt% NaOH, and resin is by Cl
-Type converts OH to
-Type.Behind deionized water rinsing, dry up standby with nitrogen.
Purify amine liquid with resin, regeneration cycle 100 times, amine liquid uses 30% oil plant desulfurizer amine liquid of heat stable salts content 5%~10%, makes resin adsorption saturated with 300~900 milliliters of amine liquid, washes resin with the NaOH of 200 milliliters of 5~20wt% and regenerates in 60 minutes.Circulate after 100 times, with the sodium chloride solution flushing of 5~20wt%, with the NaOH flushing, the resin volume obviously expands again, purifies the circulation of amine liquid again.The 1st time, the 100th time and sample of the per 50 milliliters of collections of the 101st the circular flow fluid in saline solution flushing back, the heat stable salts content in the analytic sample.Analyze data such as table 2.
Compare with fresh resin after observing resin circulation 100 times, can not recover after obvious contraction and regeneration are arranged, when handling with sodium chloride, flowing out liquid is pale brown look, and the resin volume obviously expands, and the exchange capacity of handling the back resin recovers substantially, and resuscitation effect is more obvious.
Table 2 is with before and after the sodium chloride recovery resin, and resin removes heat stable salts experimental data table:
The 1st time (HSS%) | The 100th time (HSS%) | The 101st time (HSS%) | |
50ml | 0.03 | 0.51 | 0.05 |
100ml | 0.17 | 1.67 | 0.21 |
150ml | 0.59 | 5.78 | 0.65 |
200ml | 1.45 | 6.10 | 1.58 |
250ml | 4.93 | 6.54 | 4.87 |
300ml | 6.16 | 6.85 | 6.45 |
Example 5
In amine liquid purifier shown in Figure 1, in the stainless steel bed of the high 60cm of internal diameter 25mm, add II type styrene resin (B) and purify the experiment of amine liquid, the heat stable salts content in the amine liquid is about 2~6%, with the regeneration of NaOH one-step method.When circulation 100 times and 2300 times, flow out sample of the per 50 milliliters of collections of liquid, the heat stable salts content in the analytic sample.Draw the breakthrough curve of resin, as shown in Figure 2.As can be seen from Figure 2 compare circulation for 2300 times 100 times the time, the ability that removes heat stable salts in the amine liquid of resin obviously descends.
Example 6
In amine liquid purifier shown in Figure 1, in the stainless steel bed of the high 60cm of internal diameter 25mm, add II type styrene resin (B) and purify the experiment of amine liquid, heat stable salts content in the amine liquid is about 2~5%, and 300~900 milliliters of amine liquid of each circularly purifying are with one step of NaOH method of reproduction.About 100 times of every circulation, to analyzing through the heat stable salts content in the amine liquid before and after the resin bed, each product amine liquid need mix.
The experiment situation as shown in Figure 3.As can be seen from Figure 3 II type styrene resin (B) obviously descends in the efficient that circulation removes heat stable salts in the amine liquid after 2200 times.
Getting 5 gram resins, to measure exchange capacities be 0.35eq/L, be new resin exchange capacity (1.09eq/L) 32%.
Example 7
In amine liquid purifier shown in Figure 1, in the stainless steel bed of the high 60cm of internal diameter 25mm, add acrylic resin (C) and purify the experiment of amine liquid, heat stable salts content 2~5% in the amine liquid, 300~900 milliliters of amine liquid of each circularly purifying are with the regeneration of NaOH one-step method.About 100 times of each circulation, to analyzing through the heat stable salts content in the amine liquid before and after the resin bed, each product amine liquid need mix post analysis.
The experiment situation as shown in Figure 4.As can be seen from Figure 4 the efficient of acrylic resin (C) still keeps stronger heat stable salts removal efficiency 3500 circulations.
Example 8
In amine liquid purifier shown in Figure 1, in the stainless steel column of the high 60cm of internal diameter 25mm, add acrylic resin (C) and purify the experiment of amine liquid, heat stable salts content in the amine liquid is about 3%, and 300 milliliters of amine liquid of each circularly purifying are with the regeneration of NaOH one-step method.After experiencing 3500 circulations, getting 5 gram resins, to measure exchange capacities be 0.74eq/L, be fresh resin exchange capacity (1.25eq/L) 59%.
Example 9
In amine liquid purifier shown in Figure 1, in the stainless steel column of the high 60cm of internal diameter 25mm, add acrylic acid series (C) and purify the experiment of amine liquid, heat stable salts content about 3% in the amine liquid, 300 milliliters of amine liquid of each circularly purifying, with NaOH one-step method regeneration, 100~200 circulations are with the sodium chloride solution flushing recovery of 1~20wt%, experience circulate for 3500 times after, getting 5 gram resins, to measure the exchange capacities of resins be 0.96eq/L, be new resin exchange capacity (1.25eq/L) 77%.Wash the service life that recovery can prolong resin with example 8 comparative illustration sodium chloride.
Example 10
In amine liquid purifier shown in Figure 1, in the stainless steel column of the high 60cm of internal diameter 25mm, add II type styrene resin (B) and purify the experiment of amine liquid, heat stable salts content about 2~5% in the amine liquid, 300~900 milliliters of amine liquid of each circularly purifying, with NaOH one-step method regeneration, 50~100 circulations are with sodium chloride solution flushing recovery, experience circulate for 2200 times after, getting 5 gram resins, to measure the exchange capacities of resins be 0.70eq/L, be new resin exchange capacity (1.09eq/L) 64%.Wash the service life that recovery can prolong resin with embodiment 6 comparative illustration sodium chloride.
Claims (10)
1, a kind of method with strong-base anion-exchange resin purification deterioration amine liquid is characterized in that may further comprise the steps:
A, absorption: with temperature is that 30~60 ℃ and the deterioration amine liquid handled are after filtration flowed through and are filled with the resin bed of strong-base anion-exchange resin, and the heat stable salts anion in the resin adsorption deterioration amine liquid is purified deterioration amine liquid;
B, regeneration: after treating that resin adsorption in the described resin bed is saturated, wash described resin bed, make the resin in the described resin bed obtain regeneration and recover adsorption capacity substantially with alkali metal hydroxide aqueous solution;
C, repetition above-mentioned steps a and step b;
D, recovery: whenever carry out above-mentioned steps a and step b the circulation 50~200 times after, wash described resin bed with sodium-chloride water solution, remove the organic matter and the stronger SCN of affinity that are adsorbed on the resin
-, to keep the ion exchange capacity of resin.
2, the method for purification deterioration amine liquid according to claim 1 is characterized in that described strong-base anion-exchange resin is I type styrene-divinylbenzene skeleton strong-base anion-exchange resin, II type styrene-divinylbenzene skeleton strong-base anion-exchange resin or acrylic backbone strong-base anion-exchange resin.
3, the method for purification deterioration amine liquid according to claim 1 is characterized in that described filtration treatment comprises at least with active carbon filter to filter.
4, the method for purification deterioration amine liquid according to claim 1 is characterized in that also comprising the heat stable salts analysis on Content in the gained amine liquid after described adsorption treatment, with the time of determining that the ion exchange resin adion reaches capacity.
5,, it is characterized in that described alkali metal hydroxide aqueous solution is that concentration is the sodium hydrate aqueous solution of 10~20wt% according to the method for the described purification deterioration of arbitrary claim amine liquid in the claim 1 to 4.
6, according to the method for the described purification deterioration of arbitrary claim amine liquid in the claim 1 to 4, the concentration that it is characterized in that described sodium-chloride water solution is 1~20wt%.
7, according to the method for the described purification deterioration of arbitrary claim amine liquid in the claim 1 to 4, it is characterized in that the number of described resin bed is at least two, and be arranged in parallel, with carrying out continuously of the purification that realizes deterioration amine liquid; Perhaps, the number of described resin bed is one, and intermittent operation is adopted in the purification of deterioration amine liquid.
8, according to the method for the described purification deterioration of arbitrary claim amine liquid in the claim 1 to 4, it is characterized in that described deterioration amine liquid refers to that the content of heat stable salts wherein is the aqueous solution of one or more hydramine of 1~15%, hydramine comprises MEA, diethanol amine, triethanolamine, diglycolamine, diisopropanolamine (DIPA) and methyl diethanolamine.
9, according to the method for the described purification deterioration of arbitrary claim amine liquid in the claim 1 to 4, it is characterized in that described heat stable salts anion comprises organic acid, sour gas and inorganic acid radical.
10, the method for purification deterioration amine liquid according to claim 9 is characterized in that described organic acid comprises HCOO
-, CH
3COO
-And oxalate; Described inorganic acid radical comprises SCN
-, Cl
-, S
2O
3 2-, SO
4 2-And NO
3 -Described sour gas comprises SO
2, CS
2, HCN, COS and polythionic acid.
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