CN102451598B - Composite corrosion inhibitor for carbon dioxide removing system and application thereof - Google Patents

Composite corrosion inhibitor for carbon dioxide removing system and application thereof Download PDF

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CN102451598B
CN102451598B CN201010520825.8A CN201010520825A CN102451598B CN 102451598 B CN102451598 B CN 102451598B CN 201010520825 A CN201010520825 A CN 201010520825A CN 102451598 B CN102451598 B CN 102451598B
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carbon dioxide
water
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corrosion
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CN102451598A (en
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华炜
马淳安
郦和生
陈松
李春丽
鲍林
谢文洲
王亭
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention relates to a composite corrosion inhibitor for a carbon dioxide removing system. The composite corrosion inhibitor consists of a component A, a component B and a component C, wherein the component A is selected from one of water-soluble orthovanadate, water-soluble metavanadate and a mixture of water-soluble orthovanadate or water-soluble metavanadate and water-soluble molybdate; the component B is at least one salt selected from water-soluble inorganic zinc salt and water-soluble inorganic phosphate; and the component C is an organic phosphonic acid. The corrosion inhibitor disclosed by the invention is suitable for corrosion inhibition treatment in the carbon dioxide removing system, erosion of chorine ions in the carbon dioxide removing system on equipment in use can be slowed down effectively, and a corrosion inhibition rate can be over 77 percent.

Description

A kind of composite corrosion inhibitor of carbon dioxide removal systems and application
Technical field
The present invention relates to a kind of corrosion inhibiter and application thereof of carbon dioxide removal systems, relate to a kind of composite corrosion inhibitor and the application in ethylene oxide production plant carbon dioxide removal systems thereof particularly.
Background technology
Carbon dioxide eliminating is industrially often encountered, and as in process for ethylene oxide production, exist with carbon dioxide, be separating carbon dioxide, industrial usual carbon dioxide absorption desorption system (i.e. carbon dioxide removal systems) coming carries out.Carbon dioxide absorption uses absorbing liquid based on wet chemical usually, and add a certain amount of borate and other inorganic salts with penetration enhancement, carbon dioxide is removed by from system, and absorbing liquid is then used by desorption process iterative cycles simultaneously.But owing to being mixed with a small amount of oxygen and dichloroethanes in by absorption unstripped gas, dichloroethanes high-temperature lower part in alkaline solution divides hydrolysis to produce chlorion, recycles in process at absorbing liquid, and chlorion produces accumulation, and its concentration constantly raises.Equipment due to carbon dioxide removal systems (i.e. decarbonization system) mainly uses the stainless steel of the trades mark such as 304,316, and the corrosion of existence to this kind of material of chlorion has significant facilitation.Under the trace oxygen effect existed in carbon dioxide and gas, the corrosion of the further acceleration equipment of a large amount of chlorions, makes a big impact to safe, stable, the operation efficiently of system.
BP GB1415036A and Chinese patent CN1367170A disclose in potash absorbing liquid, add potassium borate, potassium vanadate (during enforcement, vanadic anhydride and potassium hydroxide react) is activator, to improve assimilation effect, activator level is the 2-8% (potassium vanadate is 1.5-5%) of absorbing liquid.Wherein, potassium vanadate is transformed with the vanadic anhydride that valency is high, hypertoxic, there is certain oxidisability, have stainless passivation corrosion inhibition in certain concentration range, but the object of foregoing invention is to improve assimilation effect, and do not investigate on the corrosion condition of equipment and potassium vanadate on the impact of corrosion, and if potassium vanadate is improper as passivation corrosion inhibiter service condition, then corrosion can be caused to increase the weight of.Chinese patent CN101066516A discloses a kind of absorbing liquid be made up of potash and boric acid hydrogen dipotassium, but does not also note the equipment corrosion problem of absorption system, does not propose the measure solved.
Summary of the invention
The object of the present invention is to provide a kind of composite corrosion inhibitor, it has excellent corrosion resistance.
Another object of the present invention is to composite corrosion inhibitor of the present invention to be applied in carbon dioxide removal systems, to slow down the corrosion of equipment in carbon dioxide removal systems.
For achieving the above object, the invention provides a kind of composite corrosion inhibitor of carbon dioxide removal systems, it is made up of component A, B component, component C, wherein, component A is selected from a kind of salt of water-soluble orthovanadate, water-soluble metavanadate, or be water-soluble orthovanadate or water-soluble metavanadate and water-soluble molybdenum hydrochlorate mixture in one; B component is be selected from least one salt in water-soluble inorganic zinc salt and water-soluble inorganic phosphate, and component C is a kind of organic phospho acid.
Component A of the present invention both can with B component and C synergistic slow corrosion, again can as activator, promote that in carbon dioxide removal systems, solution of potassium carbonate, to the absorption of carbon dioxide, plays a multiplier effect.
Component A of the present invention is preferably the one in the mixture of water-soluble orthovanadate or water-soluble metavanadate and water-soluble molybdenum hydrochlorate.Wherein said orthovanadate is selected from sodium orthovanadate and ortho-vanadic acid potassium; Metavanadate is selected from sodium metavanadate and potassium metavanadate; Molybdate is selected from sodium molybdate and potassium molybdate.
Inorganic zinc salt of the present invention is preferably from zinc sulfate; Inorganic phosphate is preferably from calgon, sodium phosphate trimer and sodium phosphate.
Organic phospho acid of the present invention is preferably from 2-phosphate-1,2,4-butane tricarboxylate (PBTCA), 1 hydroxyethylidine diphosphonate (HEDPA), 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA) and have following general formula containing phosphonate group poly-aspartate:
Wherein R 1, R 2, R 3and R 4be H or CH independently 2-PO 3h 2, the molecular weight of poly-aspartate is 2000-20000, with PO 4the content of weighing scale organic phosphine is at least 2%.Wherein, the H in poly-aspartate on nitrogen is by CH 2-PO 3h 2what replace is more, and the content of organic phosphine is higher, and its scale-inhibiting properties is better, but the content of organic phosphine can not unrestrictedly increase, and its peak is that H in poly-aspartate on nitrogen is all by CH 2-PO 3h 2replace, organic phosphine content of the present invention is with PO 4meter is preferably 2 % by weight-11 % by weight, is more preferably 5 % by weight-11 % by weight.
The phosphonate group poly-aspartate that contains of the present invention presses method preparation disclosed in Chinese patent CN1569922A, at this, Chinese patent CN1569922A prospectus is introduced as a part of the present invention in full.
Total consumption of component component A of the present invention is the 1.0-4.0% of pending aqueous solution quality.
Total consumption of B component of the present invention is the 0.04-0.4% of pending aqueous solution quality.
The consumption of component component C of the present invention is the 0.02-0.2% of pending aqueous solution quality.
Using conventional procedures prepares corrosion inhibiter of the present invention, and the reinforced order of each component is unimportant, such as, component A, B component can be mixed in predetermined ratio with component C and water, can obtain required corrosion inhibiter.Also corrosion inhibiter of the present invention (or water-soluble rear) can be joined in carbon dioxide removal systems simultaneously.
Corrosion inhibiter of the present invention is applicable to the slow corrosion treatment of carbon dioxide removal systems, be specially adapted to the slow corrosion treatment of ethylene oxide device carbon dioxide removal systems, effectively can slow down in carbon dioxide removal systems that chlorion is to the corrosion of device therefor, corrosion inhibition rate can reach more than 77%.
Inventor also finds: when component A is made up of orthovanadate or metavanadate and molybdate, with the synergy of B component and C clearly, corrosion inhibition rate can improve greatly, and corrosion inhibition rate can bring up to more than 80%.
Be not containing the wet chemical of vanadate for carbon dioxide absorbent solution, as wet chemical or be potash and boratory mixed solution time, add component A and B component, C by consumption of the present invention to carbon dioxide removal systems; When being the wet chemical containing vanadate for carbon dioxide absorbent solution, the molybdate in B component of the present invention, component C and component A can be added; Or only add instant component B, C, vanadate both can be used as the promoter of carbon dioxide absorption in such absorbing liquid, can be used as again the collaborative component A of corrosion inhibiter of the present invention.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto.
In the following example, 304 stainless steady-state polarization (the sweep speed 5mV/S measured by electrochemical workstation (CHI660D/ Shanghai Chen Hua instrument company), sweep limits-0.3 ~ 0.8V), characterize the corrosion condition of 304 stainless steels in absorbing liquid by the intersection point in the Ta Feier district on negative electrode and anodic polarization curves, intersecting point coordinate is corrosion potential and corrosion current.The present invention is absorbing liquid based on the aqueous solution only containing potash and potassium borate, and the corrosion of other system is compared with it, and corrosion potential is just becoming, corrosion current diminishes to be and has corrosion inhibition.Corrosion mitigating effect is represented by corrosion inhibition rate, calculates by following formula:
Corrosion current × 100% in corrosion inhibition rate=(corrosion current in the corrosion current in base absorption liquid-inhibition system)/base absorption liquid
Embodiment 1
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, PBTCA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.Absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.02V, corrosion current 0.55 μ A.cm -2.
Embodiment 2
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, HEDPA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.64 μ A.cm -2.
Embodiment 3
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, HPAA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.65 μ A.cm -2.
Embodiment 4
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, containing phosphonate group poly-aspartate (organic phosphine content is 9.3 % by weight, prepares by the embodiment 7 of Chinese patent CN1569922A) 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.68 μ A.cm -2.
Embodiment 5
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, calgon 0.04%, HEDPA0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.02V, corrosion current 0.50 μ A.cm -2.
Embodiment 6
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, PBTCA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.68 μ A.cm -2.
Embodiment 7
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, HEDPA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.70 μ A.cm -2.
Embodiment 8
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, HPAA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.73 μ A.cm -2.
Embodiment 9
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, containing phosphonate group poly-aspartate (organic phosphine content is 7.3 % by weight, prepares by the embodiment 2 of Chinese patent CN1569922A) 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.76 μ A.cm -2.
Embodiment 10
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, calgon 0.04%, HEDPA0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.65 μ A.cm -2.
Embodiment 11
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, potassium metavanadate 1%, potassium molybdate 0.5%, zinc sulfate 0.08%, hexa metaphosphoric acid potassium 0.04%, HEDPA0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.02V, corrosion current 0.53 μ A.cm -2.
Embodiment 12
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, sodium phosphate 0.04%, HEDPA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.66 μ A.cm -2.
Embodiment 13
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, sodium phosphate trimer 0.04%, HEDPA0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.01V, corrosion current 0.74 μ A.cm -2.
Embodiment 14
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, zinc sulfate 0.08%, sodium phosphate trimer 0.04%, HEDPA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential-0.01V, corrosion current 0.92 μ A.cm -2.
Embodiment 15
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium metavanadate 1%, zinc sulfate 0.08%, sodium phosphate trimer 0.04%, HEDPA 0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential-0.04V, corrosion current 1.08 μ A.cm -2.
Embodiment 16
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1.6%, sodium molybdate 1.6%, zinc sulfate 0.08%, calgon 0.04%, HEDPA0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.02V, corrosion current 0.49 μ A.cm -2.
Embodiment 17
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.2%, calgon 0.15%, HEDPA0.05%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.02V, corrosion current 0.50 μ A.cm -2.
Embodiment 18
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, calgon 0.04%, HEDPA0.10%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.02V, corrosion current 0.51 μ A.cm -2.
Embodiment 19
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium orthovanadate 1%, sodium molybdate 0.5%, zinc sulfate 0.08%, calgon 0.04%, HEDPA0.18%.When 90 DEG C, pass into carbon dioxide and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characteristics is: corrosion potential 0.02V, corrosion current 0.51 μ A.cm -2.
Comparative example 1
The aqueous solution (base absorption liquid) composition (mass percent) is: potash 20%, potassium borate 6%.When 90 DEG C, pass into carbon dioxide wherein and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characterisitic parameters is: corrosion potential-0.15V, corrosion current 4.68 μ A.cm -2, compare the effect of different composite corrosion inhibiter.
Comparative example 2
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, potassium vanadate 1% (vanadic anhydride is dissolved in potassium hydroxide and makes).When 90 DEG C, pass into carbon dioxide wherein and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characterisitic parameters is: corrosion potential-0.10V, corrosion current 1.64 μ A.cm -2.
Comparative example 3
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, sodium molybdate 1%.When 90 DEG C, pass into carbon dioxide wherein and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characterisitic parameters is: corrosion potential-0.11V, corrosion current 1.78 μ A.cm -2.
Comparative example 4
Aqueous solution composition (mass percent) is: potash 20%, potassium borate 6%, potassium vanadate 1% (vanadic anhydride is dissolved in potassium hydroxide and makes), sodium molybdate 0.5%.When 90 DEG C, pass into carbon dioxide wherein and make to become carbon dioxide saturated absorption liquid.This absorbing liquid to 304 Corrosion of Stainless Steel characterisitic parameters is: corrosion potential-0.08V, corrosion current 1.55 μ A.cm -2.
The corrosion mitigating effect of embodiment and comparative example refers to table 1.
The various corrosion inhibiter corrosion mitigating effect of table 1

Claims (12)

1. the composite corrosion inhibitor of a carbon dioxide removal systems, it is made up of component A, B component, component C, wherein, component A is a kind of salt being selected from water-soluble orthovanadate, water-soluble metavanadate, or be water-soluble orthovanadate or water-soluble metavanadate and water-soluble molybdenum hydrochlorate mixture in one; B component is be selected from least one salt in water-soluble inorganic zinc salt and water-soluble inorganic phosphate, and component C is a kind of organic phospho acid; Described water-soluble orthovanadate is selected from sodium orthovanadate or ortho-vanadic acid potassium, and described metavanadate is selected from sodium metavanadate or potassium metavanadate, and described molybdate is selected from sodium molybdate or potassium molybdate; Described inorganic zinc salt is selected from zinc sulfate; Described inorganic phosphate is selected from sylvite or sodium salt; Described organic phospho acid be selected from 2-phosphate-1,2,4-butane tricarboxylate, 1 hydroxyethylidine diphosphonate, 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid and have following general formula containing phosphonate group poly-aspartate:
Wherein R 1, R 2, R 3and R 4be H or CH independently 2-PO 3h 2, the molecular weight of poly-aspartate is 2000-20000, with PO 4the content of weighing scale organic phosphine is at least 2%.
2. composite corrosion inhibitor according to claim 1, is characterized in that component A is the one in the mixture of water-soluble orthovanadate or water-soluble metavanadate and water-soluble molybdenum hydrochlorate.
3. composite corrosion inhibitor according to claim 1, is characterized in that inorganic phosphate is selected from hexa metaphosphoric acid potassium, PTPP, potassium phosphate, calgon, sodium phosphate trimer and sodium phosphate.
4. the composite corrosion inhibitor according to any one of claim 1-3, is characterized in that total consumption of component A is the 1.0-4.0% of pending aqueous solution quality.
5. the composite corrosion inhibitor according to any one of claim 1-3, wherein total consumption of B component is the 0.04-0.4% of pending aqueous solution quality.
6. composite corrosion inhibitor according to claim 4, wherein total consumption of B component is the 0.04-0.4% of pending aqueous solution quality.
7. the composite corrosion inhibitor according to any one of claim 1-3, wherein the consumption of component component C is the 0.02-0.2% of pending aqueous solution quality.
8. composite corrosion inhibitor according to claim 4, wherein the consumption of component component C is the 0.02-0.2% of pending aqueous solution quality.
9. composite corrosion inhibitor according to claim 5, wherein the consumption of component component C is the 0.02-0.2% of pending aqueous solution quality.
10. composite corrosion inhibitor according to claim 6, wherein the consumption of component component C is the 0.02-0.2% of pending aqueous solution quality.
The purposes of 11. any one composite corrosion inhibitors according to claim 1-10, is characterized in that the slow corrosion treatment corrosion inhibiter described in any one of claim 1-10 being used for carbon dioxide removal systems.
12. purposes according to claim 11, is characterized in that carbon dioxide removal systems is ethylene oxide production plant carbon dioxide removal system.
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