METHOD TO CAPTURE AN ACID GAS IN AN EXHAUST GAS

专利摘要:
building element for capturing co2 a building element for a plant for capturing an acid gas using an aqueous amine absorbent, wherein at least a portion of a surface of said element comprises a polyolefin, and a hydrolytically stable antioxidant , is described. additionally, a liner comprising said polyolefin and the hydrolytically stable antioxidant is described. The building element can be a column, a pipe, an insert, such as a column gasket element or a tray. an apparatus for capturing co2 using the building elements is also described.
公开号:BR112014000246B1
申请号:R112014000246-0
申请日:2012-07-05
公开日:2021-07-20
发明作者:Jamtvedt Svein；Øysaed Harry；Gjerp John Ole；Forsberg Frank Henning
申请人:Aker Solutions As；
IPC主号:

专利说明:

Technical Field
[001] The present invention relates to a construction element for capturing acid gases, for example CO2, a liner and pads for use in the column and an apparatus comprising the column, liner or pads. The invention also relates to piping for use in methods of capturing acid gases, eg CO2 as well as methods of capturing acid gases, eg CO2, using the columns, linings and inserts mentioned above. State of the Art
[002] The continuously increasing combustion of fossil fuels, such as coal, natural gas, and oil, has resulted in a dramatic increase in the concentration of CO2 in the atmosphere. There is overwhelming evidence that the greenhouse effect is at least partially caused by this increased concentration of CO2 and that this has already contributed to the climate changes that have taken place over the past few decades. According to simulation models, it is suspected to cause more and potentially more dramatic changes to the climate in the future.
[003] As a result, scientists, environmentalists and policymakers around the world are driving initiatives to reduce the amount of CO2 discharged into the atmosphere by the combustion of fossil fuels. One approach to take is to capture CO2 (ie prevent the release of CO2) from exhaust gases, for example from thermal power plants, before being released into the atmosphere. Captured CO2 can be injected into underground formations such as aquifers, oil wells for increased oil recovery or into depleted oil and gas wells for deposition as tests indicate that CO2 remains in the underground formation for thousands of years and it is not released back into the atmosphere.
[004] Most common CO2 capture processes are based on a gas mixture containing CO2 which is introduced, in counter-flow, to an aqueous absorbent in an absorber column. The gas leaving the absorber column is CO2 depleted. CO2 leaves the absorber column along with the absorbent. Typically the absorbent is subsequently regenerated in a regenerator column and returned to the absorber column. CO2 separated from the absorbent is sent to storage, for example, in an underground formation.
[005] Several types of aqueous absorbents are used in carbon capture processes including amines, carbonates and amino acid salts.
[006] The currently preferred sorbents for use in these processes are, however, aqueous solutions of different amines. The amines used for CO2 capture, as well as the fluids used for emission control and furnace gas treatment, however, interact with many of the materials most commonly used in the construction of the equipment that is used in the CO2 capture process. . For example, amines can cause corrosion or material degradation of equipment, particularly columns, their pellets and piping where the amines are present in significant amounts and at relatively high temperatures.
[007] Polyolefin materials, for example, polypropylene and polyethylene, are generally very resistant against amines at low and moderate temperatures, and can be used in contact with amines separately or as liners on less resistant substrates of, for example, steel , concrete, or composite materials. For application in CO2 capture plants, the required service life of a lining is more than 30 years at temperatures up to 80 °C and in amine solution (eg 30% monoethanolamine (MEA) in water or concentrations similar to other amines or mixtures of amines).
[008] The document EP 0657684 A (KERAMCHEMIE GMBH) 14.06.1995 describes the building part for chemical plants where a lining is provided on the metal surfaces as a coating against corrosion, where the lining has a layered structure comprising a resin layer inner layer is attached to a metallic supporting body, and where the inner layer is protected by one or more outer layers, the outer layer of which is a non-diffuse rubber layer.
[009] DE 2105859 A (FRACTIONATION RESEARCH LTD) 07.10.1971 refers to building elements for chemical process plants made of high temperature polypropylene without any organic metal compounds at least in the surface layer. Said building elements are said to be resistant to water and many chemicals.
[0010] DE 3820434 A (LINDE AG) 21.12.1989 refers to an absorption column having a gasket comprising gasket elements made of polymers such as polypropylene or polyethylene. Nothing is said about the nature of polymers, or their use as a lining.
[0011] DE 102009013757 A (LINDE AG) 29.09.2010 describes an absorption column for capturing CO2 including a gasket made of synthetic material such as plastic. Nothing is discovered about the nature of the synthetic material.
[0012] US 2006/0156923 A (BASF AG) 20.07.2006 discloses the idea of using a polypropylene liner in an inert scrambling column to deacidify acid gases. Additionally, MOSER, Peter, et al. Material Testing for Future Commercial Post-Combustion Capture Plants -. Energy Procedia.Sep 2010, vol. 4, p. 1317 1322. test the performance of a polypropylene-lined concrete module in a flow line that returns absorbent to an absorption column. No details on the nature of polypropylene are, however, disclosed in the publication.
[0013] MÜLLER, Werner W., et al. Antioxidant depletion and eight values of high impact PP strands. Chinese Journal of Polymer Science. 2009, vol. 27, no. 3, p. 435 445. refers to a study of depletion of different antioxidants in polypropylene (PP) during immersion in water, and water inversion combined with aging in an air oven. There is, however, no mention of the effects of aqueous solutions as such, or more specifically aqueous amine solutions used as CO2 absorbers on antioxidants, or on PP including antioxidants.
[0014] The requirements for the useful life, or service life, of building elements in contact with aqueous amine solutions in a plant for the capture of CO2, such as columns, tanks, piping, gasket etc., is 30 years. The depletion of antioxidants used to stabilize polyolefins under exposure to operating conditions whose building element comprising a polyolefin will be exposed is an indication of the useful life for the polyolefin. Testing at temperatures higher than the expected operating temperature until degradation or mechanical breakdown of the polyolefin material is an accepted accelerated test that can give a better indication of service life.
[0015] The tests described by Müller et al, see table 3, indicate that antioxidants such as Irganox 1010 and Irganox 1330 are depleted within 120 days in a water bath at 90 °C, and 301 days at 90 °C. Even though it is indicated that, for the Irganox 1330 antioxidant, the OIT values during aging changed more slowly than the reduction of antioxidant concentration in the polymer, the shelf life for a polyolefin stabilized with Irganox 1330 is assumed from the data provided by Müller et al, is much shorter than 30 years. The subject matter expert reading Müller et al would conclude that antioxidants other than Irganox 1330 had to be used to provide the required shelf life.
[0016] The candidate material, beta (b)-PP BE60-7032 from Borealis AS and, sold by Steuler as a corrosion resistant polymer, was subjected to long-term testing under conditions representative for the conditions in an absorption column of CO2. It has been found not to have the long-lasting strength required of the absorbent. This test is shown in the examples section.
[0017] For this reason, there is a need to develop stronger materials for long-term operation to build equipment for use in CO2 capture plants. Additional goals for the present invention will be apparent to one skilled in the art upon reading the description. Description of the Invention
[0018] According to a first embodiment, the present invention relates to a building element for a plant for capturing an acid gas using an aqueous amine absorbent, wherein at least a part of a surface of said element comprises a polyolefin, wherein the polyolefin composition comprises a hydrolytically stable antioxidant stable in amine solutions, of formula (I) or (II),
wherein R1 is C1-18 alkyl, C5-12 cycloalkyl, phenyl or C7-9 phenylalkyl; R2is hydrogen, C1-18 alkyl, C5-12 cycloalkyl, phenyl or C7-9 phenylalkyl; R3 is hydrogen or methyl; R4 is (a), (b), (c) or (d)
and R5 is hydrogen or phenyl.
[0019] Polyolefins stabilized by the identified group or antioxidants have shown, in tests, to be very promising for long-term use to build building elements for plants to capture CO2, as tests indicate that these polymers can have a shelf life of 30 years or more in the extremely challenging environment found within the columns, pipes etc of such plants.
An especially preferred antioxidant is 1,3,5-tri-methyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene. This antioxidant has been extensively tested after giving promising preliminary results.
[0021] The polyolefin may be a polypropylene polymer, such as a polypropylene homopolymer, optionally comprising a beta-crystalline phase. Alternatively, the polyolefin can be an ethylene polymer.
[0022] According to one modality, the synthetic hydrotalcite is added to the polymer mixture. Hydrotalcite is assumed to have a positive effect on the service life of a polyolefin in amine solutions at the operating temperatures of a CO2 capture plant. Additional testing is performed to confirm the assumption.
According to an embodiment, the surface of the building element expected to be exposed to the aqueous amine absorbent, amine vapor and/or vapor is coated with said polyolefin composition. Alternatively, the surface of the building element which is expected to be exposed to the aqueous solution of amine, vapor thereof or steam is a liner comprising said polyolefin composition which is attached to the surface of the building element. The coating or lining will, under these modalities, protect the underlying structures from exposure to amine solutions. Aqueous amine solutions are extremely corrosive and by protecting the underlying structure with a polymer coating or polymer liner in accordance with the present invention, materials that are not resistant to corrosion by the amine solution are protected from exposure, making it possible use simpler and less expensive materials to build the plant.
[0024] Examples of building elements according to the present invention are an absorption column, a desorption column, a tube, a liner, a tray, or a column gasket element. All of said elements are exposed to hot amine solutions and a coating or liner comprising the present polyolefin blend may be beneficial. Brief Description of Drawings
[0025] Figure 1 is a schematic diagram of an absorption column
[0026] Figure 2 is a schematic diagram of a capture process
[0027] Figure 3a shows the depletion of IRGANOX 1010 from a commercially available PP exposed to 30% aqueous MEA solution over time and Figure 3b is an Arrhenius plot to predict the shelf life at any given temperature of the PP
[0028] Figure 4 shows microscopic images of an (a) unaged sample and (b) aged sample of commercially available PP material
[0029] Figure 5 shows the DSC curves of (a) unaged sample and ((b) and (c)) aged samples of commercially available PP
[0030] Figures 6a and 6b show the depletion of IRGANOX 1010+IRGANOX 1330 from a polyolefin composition of the invention exposed to the new 30% aqueous MEA solution and 2-amino-2-methyl-1-propanol aqueous solution ( AMP) and 1-(2-aminoethyl)-piperazine (AEP) used over time and 6c is an Arrhenius plot to predict the shelf life at any given temperature of the polyolefin composition.
[0031] Figure 7a separately shows the depletion of IRGANOX 1010 and IRGANOX 1330 from a polyolefin composition of the invention exposed to the novel 30% aqueous MEA solution over time and Figure 7b is a plot of Arrhenius determining to predict the service life at any given temperature of the polyolefin composition
[0032] Figure 8 shows microscopic images of an unaged sample and aged sample of polyolefin composition plates used in the present invention
[0033] Figure 9 shows the DSC curves of unaged samples and aged samples of polyolefin composition used in the present invention.
[0034] Figure 10 illustrates the depletion of IRGANOX1010 and IRGANOX 1330 in hot amine solution,
[0035] Figure 11 are figures of test specimens after a period of aging,
[0036] Figure 12 illustrates the change in tensile modulus and breaking strength as a function of sample aging,
[0037] Figure 13 illustrates fracture surfaces of test specimens after aging in amine solution,
[0038] Figure 14 illustrates the depletion of IRGANOX1010 as a function of time embedded in different solutions, and
[0039] Fig 15 illustrates the depletion of IRGANOX1330 as a function of time embedded in different solutions. Detailed Description Definitions
[0040] By the term building element is meant any element forming a part of a plant according to the present invention that is in contact with aqueous amine solutions, and/or amine steam and steam, such as columns, piping, elements of gasket for columns and similar, etc.
[0041] By the term column is meant any elongated structure that has a body, at least one inlet and at least one outlet. The column can be any shape, for example cylindrical or oblong.
[0042] By the term "acid gas" is meant a gas that when dissolved in water produces a pH of less than 7.
[0043] By the term "polyolefin" is meant herein a polymer comprising units derived from an alkene. Preferred polyolefins are C2 and C3 polyolefins which comprise units derived from ethylene and/or propylene respectively.
[0044] By the term "ethylene polymer" is meant herein a polymer comprising at least 50 mol% of units derived from ethylene.
[0045] By the term "propylene polymer" is meant herein a polymer comprising at least 50 mol% of units derived from propylene.
[0046] The terms "ethylene homopolymer" and "propylene homopolymer" are intended to encompass polymers consisting essentially of repeating units deriving from ethylene or propylene respectively. Homopolymers may, for example, comprise at least 99%, for example 100%, by weight of repeat units deriving from ethylene or propylene as appropriate.
[0047] The term "ethylene copolymer" is intended to encompass polymers comprising repeating ethylene units and at least one other monomer. In typical copolymers at least 1%, more preferably at least 2% by weight of repeat units are derived from at least one monomer other than ethylene.
[0048] The term "propylene copolymer" is intended to encompass polymers comprising repeating units of propylene and at least one other monomer. In typical copolymers at least 1%, more preferably at least 2% by weight of repeat units are derived from at least one monomer other than propylene.
[0049] By the term "antioxidant" is meant an agent that is capable of inhibiting radical reactions in a polyolefin and thus preventing degradation processes.
[0050] By the term "hydrolytically stable antioxidant" is meant an antioxidant that has a half-life of at least 3 years at pH7 at 25 oC (EPIWIN HIDROWIN v1.67) program. acid gas
[0051] The acid gas can be, for example, CO2, H2S, SO2, CS2, HCN, COS, NO2 or mercaptans. More often, however, the acid gas will be CO2. Gas is usually present in the exhaust of oxidation reactions such as the combustion of coal, organic waste or oil. Aqueous amine absorbent
[0052] The aqueous amine absorbent used to capture acid gases may comprise an aqueous solution of any amine that is proposed or has been used for capturing acid gases such as CO2. Examples of suggested amines for capturing acid gases can be found, ie, in US 7585479 B (INSTITYTE FRANCAIS DU PETROE) 08.08.2009. Exemplary amines that are tested in connection with the present invention are AMP (2-amino-2-methyl-1-propanol), AEP (aminoethylpiperazine), MEA (monoethanolamine), piperazine, and combinations thereof. Polyolefin
[0053] Preferably the polyolefin is an ethylene polymer or a propylene polymer, more preferably a propylene polymer. Propylene Polymer Properties
[0054] The propylene polymer present in the composition used in the invention preferably comprises at least 80 mol% of units derived from propylene. Even more preferably the propylene polymer comprises at least 95 mol% units, especially preferably at least 99 mol% units derived from propylene (eg 97 to 99.9 mol% units derived from propylene).
[0055] The propylene polymer may comprise units of one or more other monomers. Units may, for example, be present which are derived from α-olefins having 2 or 4-10 carbon atoms. Examples of suitable monomers include ethylene, but-1-ene, pent-1-ene, hex-1-ene and oct-1-ene. Ethylene and butene are preferred.
[0056] Preferred propylene polymers comprise less than 40 mol% of units deriving from α-olefin having 2 or 4-10 carbon atoms. Still further preferred propylene polymers comprise less than 20 mol%, especially preferably less than 10 mol%, for example less than 5 mol% of units deriving from α-olefin having 2 or 4-10 atoms of carbon. Particularly preferred propylene polymers consist essentially (for example, consist of) of units derived from propylene.
[0057] Even more preferably the propylene polymer is a homopolymer. Propylene homopolymer has excellent chemical resistance as well as high thermal resistance. It is thus preferred to use in the present invention.
[0058] The propylene polymer preferably has a density of 855 to 946 kg/m3, more preferably 900 to 920 kg/m3, even more preferably 902 to 905 kg/m3.
[0059] The propylene polymer preferably has a melt flow rate (MFR2) in the range 0.01 to 100 g/10 min, preferably 0.05 to 20 g/10 min, more preferably 0.1 to 2 g/min 10 min. Preferably the melt flow rate (MFR2) of the propylene polymer is less than 2 g/10 min.
[0060] The propylene polymer preferably has a melting point in the range 130 to 171 oC, more preferably 140 to 165 oC, even more preferably 140 to 150 oC (eg around 150 to 165 oC).
[0061] The propylene polymer is preferably partially crystalline, for example, having a crystallinity of the order of 30 to 70%, for example, from 45 to 60%. Particularly preferably the propylene polymer comprises a beta-crystalline phase. Preferably 30-100%, more preferably more than 50%, even more preferably more than 80% of the crystalline phase present in the final product is in beta form. The presence of crystals in beta form has been found to improve the chemical resistance of the polymer.
[0062] The propylene polymer used in the invention is preferably homogeneous in structure (eg, free gel). Preferably the propylene polymer is soluble in decalin at 135°C. Preferably the molecular weight distribution (MWD) of the propylene polymer is in the range from 2 to 20, more preferably from 2.5 to 8, even more preferably from 3 to 7, e.g. about 3.5 to 6.5 .
[0063] The propylene polymer can be unimodal or multimodal (eg, bimodal) with respect to the molecular weight distribution. The molecular weight profile of a multimodal polymer does not consist of a single peak, but rather comprises the combination of two or more peaks (which may or may not be distinguishable) centered around different average molecular weights as a result of the fact that that the polymer comprises two or more separately produced components.
[0064] When the propylene polymer is multimodal, its components can be propylene homopolymers or propylene copolymers. Preferably, however, in such polymers the propylene polymer components are different copolymers. In multimodal propylene polymers at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 40% by weight of each propylene component (eg homopolymer and copolymer) is present based on the total weight of the polymer.
[0065] Preferably the propylene polymer of the present invention is unimodal with respect to molecular weight distribution.
[0066] Propylene polymers suitable for use in the invention are commercially available. For example, b-PP BE60-7032 is commercially available from Borealis AS.
[0067] Alternatively, the propylene polymer can be prepared by polymerization processes known in the art. Ethylene Polymer Properties
[0068] The ethylene polymer present in the composition of the invention preferably comprises at least 80 mol% of units derived from ethylene. Even more preferably the ethylene polymer comprises at least 95 mol% units, especially preferably at least 99 mol% units derived from ethylene (eg from 97 to 99.9 mol% units derived from of ethylene).
[0069] The ethylene polymer may comprise units of one or more other monomers. Units may, for example, be present which are derived from α-olefins having 3-10 carbon atoms. Examples of suitable monomers include propylene, but-1-ene, pent-1-ene, hex-1-ene and oct-1-ene. Propylene and butene are preferred.
[0070] Preferred ethylene polymers comprise less than 40 mol% of units deriving from α-olefin having 3-10 carbon atoms. Even more preferred ethylene polymers comprise less than 20 mol%, especially preferably less than 10 mol%, for example less than 5 mol% of units deriving from α-olefin having 3-10 carbon atoms . Particularly preferred ethylene polymers consist essentially (for example, consist of) of units derived from ethylene.
[0071] Even more preferably the ethylene polymer is a homopolymer.
[0072] The ethylene polymer preferably has a density of 925 to 970 kg/m3, more preferably 940 to 965 kg/m3, even more preferably 960 to 965 kg/m3.
[0073] The ethylene polymer preferably has a melt flow rate (MFR2) in the range of 0.0001 to 50 g/10 min, preferably 0.001 to 10 g/10 min, more preferably 0.005 to 1 g/10 min min. Preferably the melt flow rate (MFR2) of the ethylene polymer is less than 0.5 g/10 min.
[0074] The ethylene polymer preferably has a melt flow rate (MFR5) in the range of 0.001 to 200 g/10 min, preferably 0.01 to 50 g/10 min, more preferably 0.05 to 5 g /10 min. Preferably the melt flow rate (MFR5) of the ethylene polymer is less than 1 g/10 min.
[0075] The ethylene polymer preferably has a melting point of more than 110 oC, more preferably more than 120 oC, even more preferably more than 125 oC (eg around 128 to 132 oC). The maximum melting point of the ethylene polymer can be 150 °C.
[0076] The ethylene polymer is also preferably partially crystalline, for example, having a crystallinity of the order of 40 to 80%, for example, from 60 to 70%.
[0077] The ethylene polymer of the invention is preferably homogeneous in structure (eg, free gel). Preferably the ethylene polymer is soluble in decalin at 135°C. Preferably the MWD of the ethylene polymer is in the range from 2 to 20, more preferably from 3 to 10, even more preferably from 3.5 to 8, for example about 4 to 7.
[0078] The ethylene polymer can be unimodal or multimodal (eg bimodal) with respect to the molecular weight distribution. The molecular weight profile of a multimodal polymer does not consist of a single peak, but rather comprises the combination of two or more peaks (which may or may not be distinguishable) centered around different average molecular weights as a result of the fact that the polymer comprises two or more separately produced components.
[0079] When the ethylene polymer is multimodal, its components can be ethylene homopolymers or ethylene copolymers. Preferably, however, in such polymers the ethylene polymer components are different copolymers. In multimodal ethylene polymers at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 40% by weight of each ethylene component (eg homopolymer and copolymer) is present based on the total weight of the polymer.
[0080] Preferably, the ethylene polymer of the present invention is multimodal with respect to molecular weight distribution.
[0081] Ethylene polymers suitable for use in the invention are commercially available. For example, BS2581 is commercially available from Borealis AS. Alternatively ethylene polymer can be prepared by polymerization processes known in the art. Mechanical properties of polyolefin
[0082] The mechanical properties of the polyolefin used in the present invention are preferably as follows:
[0083] The tensile modulus (1 mm/min) of the polyolefin (eg ethylene or propylene polymer) is preferably in the range 500-5000 MPa, more preferably 800-3000 MPa, even more preferably 1000-2000 MPa. The yield strength (50 mm/min) of the polyolefin is preferably in the range of 2-25%, more preferably 5 to 15%, even more preferably 8-12%. The yield strength in yield (50 mm/min) of the polyolefin is preferably in the range of 5100 MPa, more preferably 15-50 MPa, even more preferably 20-40 MPa.
[0084] The heat deflection temperature (Method B - 0.45MPa) of the polyolefin (eg ethylene or propylene polymer) is preferably in the range 70-150 oC, more preferably 80-130 oC, even more preferably 90 -120oC.
[0085] The softening temperature of Vicat A50 (10N) of the polyolefin (eg ethylene or propylene polymer) is preferably in the range of 80-170°C, more preferably 100-165°C, even more preferably 120-160°C.
[0086] The Charpy impact power, grooved (23 oC) of the polyolefin (eg ethylene or propylene polymer) is preferably in the range of 1-100 kJ/m2, more preferably 25-75 kJ/m2, even more preferably 40 60 kJ/m2.
[0087] The Charpy impact power, slotted (-20 oC) is preferably in the range of 1-10 kJ/m2, more preferably 2.5-7.5 kJ/m2, even more preferably 4-6 kJ/m2 for propylene polymer and in the range 1-40 kJ/m2 more preferably 5-35 kJ/m2 even more preferably 10-30 kJ/m2 for ethylene polymer. Polyolefin Stabilization
[0088] Polyolefins readily undergo reactions with oxygen. Such oxidation reactions are of vital interest as the result can be molecular chain excision and as a result reduced mechanical properties. Technically such oxidation reactions are often referred to as polyolefin degradation.
[0089] The degradation of polymers can be influenced both chemically (eg by water, acids, amines and oxygen etc) and physically (eg by heat, UV light, high energy irradiation or mechanical energy). The primary factors determining the degree of polyolefin degradation over its service life are temperature, ambient and polyolefin stabilization. The polyolefins used in the present invention are exposed to aqueous solutions of amines, such as MEA, at temperatures of 60-100°C for extended periods of time, ideally 30 years. This exposure places a high demand on the polymer's resistance to degradation.
[0090] The service life of the polyolefin used in the present invention is significantly improved using a particular antioxidant, and especially using a specific combination of antioxidants and stabilizers. Without wishing to be bound by theory, it is believed that the service life of the polyolefin used in the present invention is primarily determined by the antioxidants and stabilizers added thereto. Thus it is hypothesized that until the antioxidants/stabilizers are consumed the polyolefin will be protected from harmful oxidation and the mechanical properties of the polyolefin will remain unchanged during this period. On the other hand, as soon as all antioxidants/stabilizers are consumed the oxidation reactions will accelerate resulting in a relatively rapid reduction in mechanical properties. The presence of antioxidants which are hydrolytically stable in the polyolefin composition is therefore an important feature of the present invention. Hydrolytically Stable Antioxidants
[0091] The composition used in the present invention comprises a hydrolytically stable antioxidant. Preferred hydrolytically stable antioxidants have a half-life of at least 5 years, more preferably 10 years, even more preferably 15 years at pH 7 at 25°C (EPIWIN HIDROWIN v1.67) program. Even more preferably the hydrolytically stable antioxidant used in the present invention has a half-life of at least 1 year, more preferably 2 years, even more preferably 5 years at pH 8 at 25°C (EPIWIN HIDROWIN v1.67) program. There is no upper limit on the half-lives of hydrolytically stable antioxidants. It could be, for example, 50 years at pH 7 and 40 years at pH 8.
[0092] Preferably, the antioxidant used in the invention comprises a hydrolytically stable antioxidant of formula (I) or (II)
where phenylalkyl; R2is hydrogen, C1-18 alkyl, C5-12 cycloalkyl, phenyl or C7-9 phenylalkyl; R3 is hydrogen or methyl; R4 is (a), (b), (c) or (d)
hydrolytically stable
[0093] Preferred hydrolytically stable antioxidants are those wherein R1 is tert-butyl, cyclohexyl or phenyl, especially tert-butyl.
[0094] Additional hydrolytically stable antioxidants are those where R2 is hydrogen, tert-butyl, cyclohexyl or phenyl, especially tert-butyl.
[0095] Preferred additional hydrolytically stable antioxidants are those where R3 is hydrogen.
[0096] Still further preferred hydrolytically stable antioxidants are those wherein R4 is group (a), (b) or (c), especially (a).
Particularly preferred hydrolytically stable antioxidants are those of formula (I).
[0098] An especially preferred hydrolytically stable antioxidant is one of the following formula:

This hydrolytically stable antioxidant, 1,3,5-tri-methyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene, is commercially available from BASF under trade name Irganox 1330 or Albemarle under the trade name Etanox 330 (abbreviation IRGANOX 1330). Synthetic hydrotalcite
The composition used in the present invention preferably comprises hydrotalcite, particularly synthetic hydrotalcite (SHT). SHT is also sometimes referred to as an anionic clay or a double layer hydroxide. In SHT magnesium cations are octahedrically surrounded by six oxygens in the form of hydroxides; the octahedral units then, through edge sharing, form infinite blades. The slides are stacked on top of each other via hydrogen bonding. When some of the magnesium in the lattice is isomorphically replaced by a more charged cation, eg Al3+, then the resulting global Mg2+- A13+ - OH layers gain a positive charge. Counteranions in carbonate form are also often present. Usually SHT is in hydrated form.
[00101] A typical hydrotalcite can be represented by the formula Mg1-xAlx(CO3)x/2(OH)2. mH2O where 0<x<0.5. Preferably, the hydrotalcite is of the formula Mg4,5Al2(CO3)(OH)13. 3.5H2O.
Preferably, the hydrotalcite has a density in the range 1 to 5 g/cm3, more preferably 1.5 to 3 g/cm3.
Preferably, the hydrotalcite present in the composition of the present invention has an average particle size of 0.1 to 1 mm, more preferably 0.2 to 0.8 mm, even more preferably 0.30 to 0.60 mm. Preferably at least 75% by volume of the particles are less than 1 mm in size, even more preferably at least 80% by volume of the particles are less than 1 mm in size, even more preferably at least 85% by volume of the particles are less than 1mm in size.
[00104] Particularly preferably the hydrotalcite present in the composition of the present invention is coated with a surfactant.
Preferably, the hydrotalcite present in the composition of the present invention has a hardness from 1 to 5 Mohs, more preferably from 1.5 to 3 Mohs.
[00106] Synthetic hydrotalcite for use in the present invention is commercially available from, for example, Kyowa Chemical Industry Co. as DHT-4A or DHT-4V. Heat stable antioxidant
[00107] The composition used in the present invention preferably comprises a heat stable antioxidant. Preferred heat-stable antioxidants are phenolic compounds of general formula (IIIa): HO-(R1R2R3R4Phenyl)-W (IIIa) wherein R1and R4are in position 2 and 6 of the phenol residue, may be the same or different and are selected from from the group consisting of C1 to C12 alkyl; R2and R3are independently H or C1-12 alkyl; and W is selected from C1 to C12 alkyl, C1 to C12 alkoxy, C1 to C12 alkyl carboxylate or C1 to C12 alkyl substituted by an additional group of the formula HO- (R1R2R3R4Phenyl)-, wherein R1 to R4 are as they were defined earlier in this document.
[00108] In preferred compounds of formula (IIIa), R1 and R4 are the same. Particularly preferably R1 and R4 are branched alkyl. Particularly preferably R1 and R4 are selected from tert-butyl, iso-propyl, cyclohexyl, cyclopentyl and adamantyl.
[00109] Additional preferred heat-stable antioxidants are those of formulas (IIIb)
wherein R1is C1-18 alkyl, C5-12 cycloalkyl, phenyl or C7-9 phenylalkyl; R2is hydrogen, C1-18 alkyl, C5-12 cycloalkyl, phenyl or C7-9 phenylalkyl; R3 is hydrogen or methyl; n is 0 or an integer from 1 to 6; ep is an integer from 2 to 6.
Preferred heat-stable antioxidants of formula (IIIb) are those wherein R1 is tert-butyl, cyclohexyl or phenyl, especially tert-butyl.
Further preferred heat stable antioxidants of formula (IIIb) are those wherein R2 is hydrogen, tert-butyl, cyclohexyl or phenyl, especially tert-butyl.
[00112] Additional preferred heat-stable antioxidants of formula (IIIb) are those wherein R3 is hydrogen.
[00113] Still further preferred heat stable antioxidants of formula (IIIb) are those wherein n is 1, 2 or 3, especially 2.
Still further preferred heat-stable antioxidants of formula (IIIb) are those wherein p is 4.
[00115] Representative examples of heat-stable antioxidants that may be present in the compositions of the invention include: - 2,6-Di-tert-butyl-4-methyl phenol; - Pentaerythryl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate; - Octadecyl 3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate ; - 1,3,5-Trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene; - 2,2'-Thiodiethylene-bis-(3,5- di-tert-butyl-4-hydroxyphenyl)-propionate; - Calcium-(3,5-di-tert-butyl-4-hydroxy benzyl monoethyl-phosphonate); - 1,3,5-Tris(3',5 '-di-tert-butyl-4'-hydroxybenzyl)-isocyanurate; - Bis-(3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid glycolester); - 4,4' -Thiobis(2-tert-butyl-5-methylphenol); - 2,2'-Methylene-bis(6-(1-methyl-cyclohexyl)para-cresol); - N,N'-hexamethylene bis(3,5 -di-tert-Butyl-4-hydroxy-hydrocinnamamide; - 2,5,7,8-Tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol; - 2,2'-Ethylidenebis (4,6-di-tert-butylphenol); - 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; -1,3,5-Tris(4-tert- butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; -3,9-Bis(1,1-dimethyl- 2-(beta-(3-tert-butyl-4-hydroxy-5-methylphen yl)propionyloxy)ethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane; - 1,6-Hexanediyl-bis(3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoate); - 2,6-Di-tert-butyl-4-nonylphenol; - 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6(1H,3H,5H)-trione; - 4,4'-Butylidenebis(6-tert-Butyl-3-methylphenol); - 2,2'-Methylene bis(4-methyl-6-tert-butylphenol); - 2,2-Bis(4-(2-(3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy))ethoxyphenyl))propane; - triethylene glycol bis-(3-tert-butyl-4-hydroxy-5 methylphenyl) propionate; - Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C13-C15-branched and linear alkyl esters; - 6.6'-Di-tert-butyl-2,2'-thiodi-p-cresol; - Diethyl((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl) phosphonate; - 4,6-Bis(octylthiomethyl)o-cresol; - Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)4-hydroxy-, C7-C9-branched and linear alkyl esters; - 1,1,3-Tris[2-methyl-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyloxy]-5-t-butylphenyl]butane; and - a butylated reaction product of p-cresol and dicyclopentadiene. Preferred heat stable antioxidants are: - Pentaerythryl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate; -3-(3',5'-di-tert-butyl- octadecyl 4-hydroxyphenyl)propionate; -1,3,5-Trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene; -1,3,5-Tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-isocyanurate; -Bis-(3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid glycolester); and - 3,9-Bis(1,1-dimethyl-2-(beta-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl)-2,4,8,10-tetraoxaspiro (5 .5) undecane;
[00116] An especially preferred heat-stable antioxidant is one of the following formula:

[00117] This heat stable antioxidant is commercially available from BASF under the trade name Irganox 1010 (abbreviation IRGANOX 1010). Phosphonite or organic phosphate antioxidant
[00118] The composition used in the present invention preferably comprises an antioxidant of phosphonite or organic phosphite. Preferred phosphonite or organic phosphite antioxidants are those of formulas (IVa) bis(R1)-pentaerythritol diphosphite (IVa), wherein R1 is selected from C1-C25 alkyl group or C6-10 aryl group optionally substituted by C1-6 alkyl.
[00119] Additional preferred phosphonite or organic phosphite antioxidants are those of formulas (IVb)
/ (IVb) where Y is a direct bond or -O-; and R 1 , R 2 and R 3 are independently selected from substituted or unsubstituted alkyl having 1-30 carbons, substituted or unsubstituted cycloalkyl having 5 to 12 carbons, substituted or unsubstituted aryl having 6 to 10 carbons, or a group of the formula (V)
4 where m is an integer in the range 1 to 3; and R4and R5are independently C1-18 alkyl or C5-12 cycloalkyl.
[00120] Substituents optionally present in R1, R2and R3 groups are preferably selected from halogen, C1-6 alkyl, C1-6 alkoxy or COOC1-6. Particularly preferably the substituents are C1-6 alkyl, for example tert-butyl.
[00121] Preferred groups of formula (V) are those wherein R4 and R5 are C1-18 alkyl, more preferably C1-6 alkyl, for example C4 alkyl. Preferably R4and R5are tert-butyl.
Preferred phosphonite or organic phosphite antioxidants are those of formulas (IVb) wherein Y is -O-.
Further preferred organic phosphonite or phosphite antioxidants are those of formulas (IVb) wherein R2 and R3 are substituted or unsubstituted aryl, particularly substituted aryl, e.g. phenyl. Preferred substituent groups are C1-6 alkyl, for example tert-butyl.
Further preferred organic phosphite or phosphonite antioxidants are those of formulas (IVb) wherein R1 is substituted or unsubstituted aryl, particularly substituted aryl, e.g. phenyl. Preferred substituent groups are C1-6 alkyl, for example tert-butyl.
[00125] Representative examples of phosphonite or organic phosphite antioxidants that may be present in the compositions of the present invention include: - Tris (2,4-di-t-butylphenyl) phosphite; - Tetrakis-(2,4-di-t-butylphenyl)-4,4'-biphenylen-di-phosphonite - Bis(2,4-di-t-butylphenyl)-pentaerythryl-di-phosphite; - Di-stearyl-pentaerythryl-di-phosphite; - Tris-nonylphenyl phosphite; - Bis(2,6-di-t-butyl-4-methylphenyl)pentaerythryl-diphosphite; - 2,2'-Methylenebis(4,6-di-t-butylphenyl)octyl-phosphite; - 1,1,3-Tris(2-methyl-4-ditridecyl phosphite-5-t-butylphenyl)butane; - 4,4'-Butylidenebis(3-methyl-6-t-butylphenyl-di-tridecyl) phosphite; - Bis(2,4-dicumylphenyl)pentaerythritol diphosphite; - Bis(2-methyl-4,6-bis(1,1-dimethylethyl)phenyl)phosphorous acid ethylester; - 2,2',2'-Nitrile triethyl-tris(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl)phosphite); - Phosphorous acid, cyclic butylethyl propandiol, 2,4,6-tri-t-butylphenyl ester; - Bis (2,4,6-tri-t-butylphenyl)-pentaerythryl-diphosphite; - 2,2'-Ethylidenebis(4,6-di-t-butylphenyl) fluorophosphonite - 6-(3-tert-Butyl-4-hydroxy-5-methylphenyl)propoxy)- 2,4,8,10-tetra- tert-butyldibenzo(d,t)(1.3.2) dioxaphosphepine; and - Tetrakis-(2,4-di-t-butyl-5-methyl-phenyl)-4,4'-biphenylenedi-phosphonite
Preferred phosphonite or organic phosphite antioxidants are: Tetrakis-(2,4-di-t-butylphenyl)-4,4'-biphenylen-di-phosphonite; Bis(2,6-di-t-butyl-4-methylphenyl)pentaerythryl-diphosphite; Di-stearyl-pentaerythryl-diphosphite; and Bis(2,4-dicumylphenyl)pentaerythritol diphosphite.
[00127] An especially preferred phosphonite or organic phosphite antioxidant is one of the following formula:

[00128] This antioxidant is commercially available from BASF under the trade name Irgafos 168 (abbreviation AO168). Sulfoether Antioxidant
[00129] The composition used in the present invention preferably comprises a sulfoether antioxidant. These antioxidants are believed to work by breaking down hydroperoxides. Preferred sulfoether antioxidants are those derived from lauric or stearic acid.
[00130] Preferred sulfoether antioxidants are di(C1-C20)alkyl-S-dicarboxylates wherein the carboxylic acid is selected from carboxylic acids of C1 to C10 alkyl.
[00131] Representative examples of sulfoether antioxidants that can be used in the compositions of the present invention include: - Di-stearyl-thio-di-propionate; - Di-palmitil/stearyl-thio-di-propionate; - Di-lauryl-thio-di-propionate; - Di-tridecyl-thio-di-propionate; - Di-myristyl-thio-di-propionate; - Octyl pentaerythritol thiodipropionate; - Lauryl-stearyl-thio-di-propionate; - Di-octadecyl-disulfide; - Di-tert-dodecyl-disulfide; and - Pentaerythritol-tetrakis-(3-laurylthiopropionate).
[00132] Pentaerythritol tetrakis(B-laurylthiopropionate) (CAS 29598-76-3)), distearyl-3,3'-thiodipropionate (CAS 693-36-7) and dilauryl-3,3'-thiodipropionate (CAS 123-28) -4) are preferred. A particularly preferred sulfoether antioxidant is distearyl-3,3'-thiodipropionate (DSTDP). It is commercially available under the tradename Irganox PS 802-FL from BASF. Blocked amine antioxidant
[00133] The composition used in the present invention preferably also comprises a sterically blocked amine antioxidant. Preferred sterically blocked amine antioxidants have a molecular weight of more than 500 g/mol.
Particularly preferred amine antioxidants for use in the compositions of the present invention comprise a radical of formulas (VI)
(VI) where G is hydrogen or methyl; G1 and G2 are hydrogen, methyl or together are =O.
[00135] An especially preferred amine antioxidant is one of the following formula:

[00136] This antioxidant is commercially available from BASF under the trade name Chimassorb 119. Other additives
[00137] The composition used in the present invention optionally comprises other conventional additives. Representative examples of suitable additives include nucleating agents (a or b, preferably b, nucleating agents), light stabilizers, dyes, antistatic agents, lubricants, carbon black and flame retardants. A filler (eg talc) may also be present. Composition preparation
[00138] The polyolefin is blended with antioxidants and optionally SHT, as well as any additional additives present in the composition, by conventional techniques, for example by blending. The preferred composition can be prepared directly by the polymer producer, that is, by 1) adding the total additive formulation to a polymer powder followed by compounding by extrusion and pelletizing, or 2) by adding the missing additives to a commercial polymer (P1) preferably via a masterbatch (MB) of additives lacking in the same polymer type as P1, or preferably adding the additives directly to P1. For both 1) and 2) the total blends are extruded to give an optimal distribution of additives in the polymer.
[00139] Preferred compositions for use in the present invention comprise a polyolefin, a hydrolytically stable antioxidant and SHT. Other preferred compositions for use in the invention comprise a polyolefin, a hydrolytically stable antioxidant and a heat stable antioxidant. Particularly preferred compositions comprise a polyolefin, a hydrolytically stable antioxidant, a heat stable antioxidant and SHT. Compositions listed as above herein further comprising a phosphonite or organic phosphite antioxidant and/or a thioether antioxidant are especially preferred.
[00140] A preferred composition for use in the present invention comprises: (i) a polyolefin, preferably a polymer of propylene; (ii) a hydrolytically stable antioxidant, preferably a compound of formulas I or II, for example Irganox 1330; (iii) synthetic hydrotalcite; (iv) a heat stable antioxidant, preferably a compound of formula III, for example Irganox 1010; (v) a phosphonite or organic phosphite antioxidant, preferably a compound of formula IV, e.g. Irgafos 168; and (vi) a thioether antioxidant, preferably distearyl-3,3'-thiodipropionate.
[00141] The amount of polyolefin, preferably a propylene polymer, present in the composition is preferably 55-99.8% by weight, even more preferably 90-99.5% by weight, for example 98-99.5% by weight Weight.
The hydrolytically stable antioxidant amount, preferably a compound of formulas I or II, present in the composition is preferably 100-10,000 pppm, even more preferably 2000-8000 pppm, for example 3000-6000 pppm.
The amount of synthetic hydrotalcite present in the composition is preferably 100-10000 pppm, even more preferably 250-5000pppm, for example 1000-3000pppm.
The amount of heat stable antioxidant, preferably a compound of formula III, present in the composition is preferably 100-10000 pppm, even more preferably 500-6000 pppm, for example 1000-4000 pppm.
The amount of phosphonite or organic phosphite antioxidant, preferably a compound of formula IV, present in the composition is preferably 100-5000 pppm, even more preferably 300-3000 pppm, for example 500-2000 pppm.
The amount of thioether antioxidant, preferably distearyl-3,3'-thiodipropionate, present in the composition is preferably 500-10000 pppm, even more preferably 1000-8000 pppm, for example 2000-6000 pppm.
The total amount of all antioxidants present in the compositions is preferably 400-35000 pppm, even more preferably 2000-25000 pppm, for example 4000-18000 pppm. composition properties
[00148] The preferred properties of the composition, as determined in accordance with the methods set out in the examples section in relation to single boards, are as follows:
[00149] The amount of hydrolytically stable antioxidant present in a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 80°C for 12 weeks is at least 75%, preferably at least 80%, more preferably at least 85% of the amount originally present. Even more preferably the amount of hydrolytically stable antioxidant present in a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 95°C for 12 weeks is at least 70%, preferably at least 75%, more preferably at least 80% of the amount originally present.
[00150] The swollen weight of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 80°C for 12 weeks is preferably less than 1%, even more preferably less than 0.5%, even more preferably less than 0.3%. Even more preferably the swollen weight of a composition after exposure to a new 30% aqueous solution of an amine, for example MEA at 95°C for 12 weeks is preferably less than 2%, even more preferably less than 1%, even more preferably less than 0.75%.
[00151] The tensile modulus of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 80°C for 12 weeks is at least 80%, preferably at least 85%, more preferably at least 90% of the tensile modulus of the unaged composition. Even more preferably the tensile modulus of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 95°C for 12 weeks is at least 75%, preferably at least 80%, more preferably at least 85% of the tensile modulus of the unaged composition.
[00152] The yield stress of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 80°C for 12 weeks is at least 85%, preferably at least 90%, more preferably at least 95% of the effort in yield of the unaged composition. Even more preferably the yield stress of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 95°C for 12 weeks is at least 80%, preferably at least 85%, more preferably at least 90% effort in yield of unaged composition.
[00153] The yield strength of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 80°C for 12 weeks is less than 150%, preferably less than 145%, more preferably less than 140% yield strength of the unaged composition. Even more preferably the yield strength of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 95°C for 12 weeks is less than 155%, preferably less than 150%, more preferably less than 145% yield strength of the unaged composition.
[00154] The strain on breaking a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 80°C for 12 weeks is at least 80%, preferably at least 85%, more preferably at least 90% of the effort in breaking the unaged composition. Even more preferably the strain on breaking a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 95°C for 12 weeks is at least 80%, preferably at least 85%, more preferably at least 90% effort in breaking the unaged composition.
[00155] The breaking strength of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 80°C for 12 weeks is at least 70%, preferably at least 75%, more preferably at least 80% of the breaking strength of the unaged composition. Even more preferably the breaking strength of a composition after exposure to a new 30% aqueous solution of an amine, eg MEA at 95°C for 12 weeks is at least 65%, preferably at least 70%, more preferably at least 75% breaking strength of the unaged composition. Application
[00156] The present invention relates to a column for capturing acid gases such as CO2. As described above this process typically involves introducing an exhaust gas containing, for example, CO2 at the bottom of an absorption column where the gas flows upstream and countercurrent to a poor absorbent (low CO2 content) in one or more sections of column contact. The contact sections may optionally comprise a random or structural gasket to increase the contact area between the absorbent and the gas. After leaving the contact sections the gas is usually flushed and then dragged through a line at the top of the column.
[00157] The rich absorbent (higher CO2 content), usually an amine, is typically collected (eg in collecting trays) and dragged by a line at the bottom of the column. It is fed to a regeneration column or deabsorber where it flows downwards and countercurrent to a flow of CO2 and water vapor. Preferably the flow of CO2 and water vapor is generated by heating a lean absorbent fraction from the bottom of the desorber through a heated steam reboiler. From the bottom of the lean absorbent desorber can be returned to the absorption column. There is preferably a wash section at the top of the desorber and CO2 and water vapor are drawn from the top of the desorber column through a line and cooled in a desorber condenser.
[00158] Both the absorption column and the regeneration column (deabsorber) are therefore exposed to amine absorbers at high temperatures and for long periods of time and thus suffer the problems of material degradation and failure described above. The column of the present invention can therefore be an absorption column or a regenerator column. More preferably, however, the column is an absorption column.
[00159] The entire inner surface of a column may comprise the polyolefin composition described above in this document. Alternatively, only a portion of the inner surface may comprise the polyolefin composition, for example, it may be that single inner surface of the column section where contact with absorbent occurs (referred to as the contact section) comprises the polyolefin composition. The surfaces of other parts present inside the column, e.g. collection plates, trays, tubing can also be coated or lined with the polyolefin composition described herein.
[00160] The column can be constructed of the polyolefin composition described above in this document. More preferably, however, the column is constructed of concrete, metal or composite material. In this case, the inner surface is formed by coating the interior of said column with said polyolefin composition. Alternatively, and preferably, the inner surface may be formed by affixing a liner comprising the polyolefin composition to the interior of said column.
[00161] In some liners the anchors for joining the liner to the column walls also comprise said polyolefin composition. Alternatively the anchors may comprise a different composition.
[00162] The liners of the present invention may be in any form conventional in the art. For example, the liners can be in the form of sheets, profiles or tubes, preferably sheets and profiles. The thickness of the liner is preferably in the range 0.5-50mm, more preferably 220mm, for example 4-12mm.
[00163] The present invention also relates to other apparatus and parts used in the acid gas capture process which are exposed to similar operating conditions as described above. This includes, for example, inserts used in the column (eg column gasket material, trays, etc) and piping.
[00164] The linings, columns, inserts, tubing and apparatus of the present invention can be used in any method of capturing an acid gas, for example, CO2. More preferably, however, they are used in methods where an amine, particularly an aqueous solution of one or more amines, is used as an absorbent.
[00165] Preferred absorbents for use are, for example, aliphatic or cycloaliphatic amines having from 4 to 12 carbons, alkanolamines having from 4 to 12 carbons, cyclic amines where 1 or 2 nitrogens together with 1 or 2 alkylene groups form rings of 5, 6 or 7 members, mixtures of the above and aqueous solutions of the above amines and mixtures. Representative examples of amines that can be used include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diethylethanolamine (DEEA), diisopropylamine (DIPA), aminoethoxyethanol (AEE), methyldiethanolamine (MDEA), piperazine (PZ), 2 -amino-2-methyl-1-propanol (AMP) and mixtures of the above and aqueous solutions of the above.
[00166] The structure of the columns, ceilings and apparatus of the present invention is conventional and as described in the prior art. Figure 1 illustrates a typical absorption column. Figure 2 illustrates a typical apparatus comprising an absorption column and a regeneration column.
[00167] Referring to Figure 1, flue gas, usually cooled, is introduced into an inlet chamber 1 at the bottom of the absorption column 2. From the inlet chamber 1, the gas flows upwards in the absorption column and countercurrent to the liquid absorbent, eg amine solution, in one or more contact sections 3, 4. The illustrated absorption column is provided with two contact sections 3, 4 serially connected, but any number of such sections may be included. After leaving the contact sections 3, 4 the gas is washed by a countercurrent flow of water in a wash section 5 to remove any amine in the gas flow. Wash water is introduced via line 6 and sprayed on top of wash section 5. Water is collected on plate 7 below wash section and removed via line 8. Water droplets in the washed gas stream are preferably removed in denebulizer section 9 before the CO2-depleted exhaust gas is drawn through line 10. Column 2 can comprise several water sections or other types of polish/wash sections on top. Typically 80-99% of the original CO2 present in the gas is removed by absorption.
[00168] The absorbent is introduced into the column via line 11 and is sprayed on top of the upper contact section 4 by means of liquid distribution means. The absorbent flows through the upper contact section 4 and is collected in an absorbent plate 12. The absorbent is drawn via line 13 and sprayed onto the upper part of the lower contact section 3. After flowing through the lower contact section 3 the absorbent and the CO2 absorbed thereto is collected from the bottom of the column and dragged via line 14.
[00169] The temperature of the absorbent in the absorption step is generally around 30 to 100 °C, when a column is used, for example, from 30 to 70 °C at the top of the column and from 30 to 100 °C at the bottom of the column . The overall pressure in the absorption step is generally from about 0.5 to 20 bara, preferably from about 0.7 to 12 bara, particularly preferably from 0.7 to 6 bara.
[00170] Referring to Figure 2 in the regeneration column 15 the absorbent rich in CO2 flows down, countercurrent to a flow of released CO2 and water vapor, optionally generated by heating some of the absorbent in a regeneration boiler 16. The lean absorbent leaves the regeneration column through an outlet 17. A portion of this lean absorbent is introduced into the regeneration boiler 16 where it is heated to produce hot absorbent and steam which is reintroduced into the regeneration column through line 18. Bottom column gives a steady state temperature gradient from bottom to top of column, where the temperature at the top is about 10 to 50 oC lower than at the bottom, depending on the actual column design. In a typical regeneration column the temperature at the bottom of the column is about 120 oC and the temperature at the top is about 10 to 50 oC lower.
The lean absorber that is not introduced into the regeneration boiler is recycled back to the absorption column 2 through line 19 and cooled in heat exchanger 20 against rich absorber in line 14. In heat exchanger 20 the relatively cool absorber rich in CO2 is heated against the relatively hot lean absorbent leaving the absorber at a temperature of about 120 oC.
[00172] The CO2 released from the absorbent and water vapor is drawn from the regenerator column through line 21. The gas in the line is cooled in a reflux condenser 22 to condense water which is separated from the remaining gas, mainly comprising CO2 in a CO2 separator 23. The CO2 entrained in line 24 can be further treated, eg drying, compression and/or deposition. Condensed water in the CO2 separator is drawn through line 25 and pumped back to the top of the regeneration column.
[00173] The columns and linings of the present invention can also be used in the methods described in document WO2008/108657, document WO2008/063079, document WO2008/130244, document US 2010/0029466, document WO2009/035340, document WO2009/108064, document WO2010/102877 and WO/2010/142716, the contents of which are incorporated by reference. Examples
[00174] The invention will now be described with reference to the following non-limiting examples. analytical tests
[00175] The values indicated in the description and examples are measured according to the following tests:
[00176] The melt flow rate (MFR) is determined in accordance with ISO 1133 and is given in g/10 min. The MFR is an indication of the melt viscosity of the polymer. MFR is determined at 230 oC for PP and 190 oC PE. The load under which the melt flow rate is determined is usually indicated as a subscript, for example MFR2 is measured under 2.16 kg of load and MFR5 is measured under 5 kg of load.
[00177] Density was measured according to ISO 1183.
[00178] The weight average molecular weight Mw and the molecular weight distribution (MWD = Mw/Mn where Mn is the number average molecular weight and Mw is the weight average molecular weight) is measured by a method based on ISO 16014 4:2003. A Waters 150CV plus instrument, equipped with refractive index detector and online viscometer was used with 3 x HT6E styragel columns from Waters (styrene-divinylbenzene) and 1,2,4-trichlorobenzene (TCB, stabilized at 250 mg/L 2, 6-Di tert -butyl-4-methyl-phenol) as solvent at 140 °C and at a constant flow rate of 1 mL/min. 500 mL of sample solution was injected for analysis. The column assembly was calibrated using universal calibration (according to ISO 16014-2:2003) with 10 narrow MWD (PS) polystyrene standards in the range of 1.05 kg/mol to 11600 kg/mol. Mark Houwink constants were used for polystyrene and polyethylene (K: 19 x10<-3> dL/g and a: 0.655 for PS, and K: 19 x10<-3> dL/g and a: 0.725 for PP). All samples were prepared by dissolving 0.5 - 3.5 mg of polymer in 4 mL (at 140 oC) of stabilized TCB (same as mobile phase) and holding for 2 hours at 140 oC and for a further 2 hours at 160 oC with occasional shaking before sampling on the GPC instrument.
[00179] The comonomer content can be determined in a known way based on determination of Fourier Transform Infrared Spectroscopy (FTIR) calibrated with 13C-NMR.
[00180] Melting temperature (Tm), crystallization temperature (Tc) and degree of crystallinity (Xc) were measured according to ISO11357. Samples were cut from compression molds, 0.2 mm films. Measurements were performed under the following conditions: Table 1


[00181] The Tm and Xc were determined from the second heating. The degree of crystallinity (Xc) was calculated using a 100% PP melting enthalpy of 209 J/g.
[00182] The beta content is measured by wide-angle X-ray diffraction (WAXD). A WAXD scan of a PP sample contains diffraction peaks from both the alpha crystalline phase (3 peaks due to the (110), (130) and (040) planes) and the beta crystalline phase (1 peak due to the (300) plane An empirical ratio of the intensity (I) of these peaks known as the K value and defined as follows is used to define the beta content: K = I(300)β/ I(300)β + I(110)α + I( 130)α + I(040)α
[00183] The tensile modulus was measured in accordance with ISO 527. The tensile strength in yield and tensile stress in yield were measured in accordance with ISO 527-2.
[00184] The heat deflection temperature was measured according to ISO-75-2.
[00185] The softening temperature of Vicat B50 (50N) was measured according to ISO 306.
[00186] Charpy impact power, grooved (23 and -20 oC) was measured according to ISO 179/1eA.
The accelerated aging of PP-H-100 and BE60-7032 with additional antioxidants 1a. Commercially available blades of PP-H-100 without anchor and having a size of approximately 20x30 cm, thickness of 8 mm were used. 1b. For the preparation of BE60-7032 with extra antioxidants, one MB with the composition; 94% BE60-7032 + 5% Irganox 1330 + 1% SHT was compounded. 10% of this MB was then added to BE60-7032 to make up the preferred composition. Precipitates with the preferred composition were then compression molded into slabs with the dimension: 70mm x 40mm x 8mm 2. Test samples were prepared using a band saw/circular saw as follows. The. For the tensile test the samples were ground to standard dog bone (type 1B multipurpose). B. For the measurement of differential scanning calorimetry (DSC); samples sliced by microtome from surface of unexposed and exposed slides (70 x10x 8mm), 0-100 μm, 1-2 mg sample weight. ç. For measuring the amount of antioxidant (AO) present; blade size: 60x60x8mm or 70x40x8mm. 3. All samples were marked with a number to ensure traceability especially for swelling calculation. 4. All test pieces were immersed in 2 liter glass containers. The samples were tied to a rack made of acid-proof stainless steel. This was done to ensure good distance between samples. 5. Containers were filled with a 30% aqueous MEA solution and were set at a temperature of 95°C, 80°C or 60°C. 6. The maximum number of samples placed in each chamber was: 8 standard dog bones, 6 test pieces of size 60x60x8 mm or 70x40x8 mm and 6 test pieces of size 70x10x8 mm. 7. No shaking was made. When testing commercially available samples PP-H-100 containing IRGANOX 1010, AO168 and DSTDP, the 30% aqueous solution of MEA to the 95 °C container was changed each week and to the 80 °C container 50% of the 30% aqueous MEA solution was replaced every week. When testing BE60-7032 samples containing IRGANOX 1010, IRGANOX 1330, SHT and DSTDP the new 30% aqueous solution of MEA or used (as described above) was used. The amine used is amine that has been used to capture CO2 for a considerable period of time in a test plant, and that contains actual amounts of amine degradation products and contaminations. For the amine used no change in solutions during the testing period was made, only refilling to ensure that all samples are covered by the liquid throughout the testing period. 8. Samples for DSC and AO measurements were taken after 1, 2, 3, 5, 8, 12 and/or 20 weeks. For the tensile test samples were measured before aging and after 8, 12 and 20 weeks. 9. DSC was performed on material taken from the surface of the slide. A 100 µm thick layer was sliced, followed by an additional 100 µm slice. Both test pieces were analyzed by DSC to assess changes in beta crystals. 10. Measurement of AO. Plates of size 6x6 cm, thickness 8mm were taken from the containers then cut/ground into powder with a size of 1mm. The powder was mixed into a homogeneous mixture, then extracted into suitable solvents. Solutions were filtered to remove dust. The solutions were then injected into an HPLC (High Performance Liquid Chromatography) machine. To ensure the quality of the results a known standard is always used together with the samples. Furthermore, the extraction technique is performed using an internal standard. 11. AO measurements were used to calculate blade life as follows:
[00188] From the HPLC results, depletion curves as a function of storage time under different storage conditions were made from the different AO. The reduction of AO as a function of time appears to be logarithmic, so from the ln (AO concs) versus time relationship, the time to [AO] = 1 ppm was calculated under the different conditions. To plot these results on an Arrhenius graph the time to AO concentration = 1 ppm is predicted at any temperature. Test Methods 1. Determining the amount of AO present in unaged samples and aged samples Method Liquid Chromatography Instrument Agilent 1100 Specimen type Single plate unless otherwise specified Chromatographic conditions: Column: C-18 Mobile phase: Gradient of Water/AcN/IPA Detector: UV, 276 nm 2. . Absorption Test Swell-According to DS/EN ISO 16101:2004 B.2.1 Absorption Swell Resistance Immersion Liquid Monoethanolamine, MEA, 30% Aqueous Solution Receptacle Heat Chamber Specimen Type 0.8 x 4 Blade x 7 cm thick Test conditions Samples are completely immersed in the liquid at the different temperatures shown. Samples are removed from the liquid, stored in an acclimatized chamber at 23°C and weighed. The mass is weighed after specified intervals Definitions % mass increase Method uncertainty: 10 % standard deviation 3. Tensile test - According to ISO 527-2 Zwick Z010 Extensometer Instrument with Macro Specimen type Multi-purpose type 1B, ground to from the plates delivered with thicknesses of 5 mm and 8 mm. Width of specimens are 10 mm. Test conditions Test speed 50 mm/min. Modulus of tension 1 mm/min Modulus of tension, MPa - (the modulus of elasticity in tension) - the slope of a secant line between 0.05% and 0.25% strength on a stress-resistance curve. Tensile effort/strength in yield, MPa / % - tensile effort/strength corresponding to the yield point (an increase in strength does not result in an increase in effort). Tensile strength at breaking, % - tensile strength corresponding to the breaking point Tensile strength at breaking, MPa - tensile strength corresponding to the breaking point 4. Investigation by microscopy Preparation equipment: Leica RM2165 (rotational microtome) Microscope: Zeiss Axiophot (Transmitted Light Microscope) Contrast Technique: Transmitted light/inches of light field. E To-plate Transmitted light/dark field 5. Differential Scanning Calorimetry DSC - Per ISO11357-3 Perkin Elmer Diamond Hyper DSC Instrument Specimen Type Compression molded slides exposed to 95 °C. Sliced by exposed blade surface microtome, 0-100 μm, 1-2 mg sample weight. Test Conditions 1. Heat 20 to 225 °C Cool 225 to 20 °C 2. Heat 20 to 225 °C Heat / Cool rate 10 °C/min Number of parallels 3 Definitions Melting temperature, Tm - Melting peak ° C Crystallization temperature, Tc - Peak of crystallization °C Enthalpy of fusion, ΔH - the heat required to melt the material at constant pressure, J/g Evaluation of commercially available material
[00189] Test of PP-H-100 plates containing IRGANOX 1010, AO168 and DSTDP
[00190] Unaged PP H-100 plates comprised the following antioxidant composition as determined by the method described: IRGANOX 1010 2680 ppm p AO168 1170 ppm p AO168-ox 370 ppm p DSTDP 4950 ppm p 1) Determination of the amount of AO present in aged samples
[00191] The amount of antioxidants present in plates aged in 30% aqueous MEA solution at different temperatures (p ppm) is shown in the table below. A0168-ox is the oxidized form of the phosphite AO168, ie the phosphate. Table 2


[00192] IRGANOX 1010 (also abbreviated AO1010) is the antioxidant with the highest reduction in concentration under all conditions, most likely due to poor hydrolytic stability under alkaline conditions.
[00193] A lifetime prediction based on IRGANOX 1010 depletion results from PP-H 100 plates (8mm thick) stored in 30% aqueous MEA at 60°C, 80°C and 95°C was also carried out .
[00194] The logarithmic relationship between concentration of IRGANOX 1010 in PP-H 100 and exposure time in 30% aqueous MEA solution at 2 different temperatures is shown in figure 3a below.
[00195] Using the results up to 8 weeks at 95 oC, a prediction of that concentration of IRGANOX 1010 = 1 ppm after 23 weeks was obtained. This was confirmed by the results obtained from the 20 week test.
Also taking the results after 20 weeks at 80°C into account the IRGANOX 1010 is expected to be 1 ppm after 72 weeks (predicted 89 weeks after 8 weeks) at 80°C.
[00197] Placing the results on an Arrhenius graph (Figure 3b) the time to AO = 1 ppm at 75°C was calculated to be about 150 weeks (3 years) for PP-H-100 in aqueous MEA solution at 30%. However, some factors that can increase the shelf life are: (i) some of the hydrolyzed IRGANOX 1010 may have an antioxidant effect, (ii) in this study the plates were exposed to amine from both sides while under operating conditions, exposure will only occur on one side and (iii) the polyolefin that does not have AO will still have some useful life.
[00198] These results show that taking all factors into account a useful life of 8 mm thick PP H-100 blades, continuously exposed by 30% aqueous MEA solution at 75 °C, on one side, is predicted to whether in the 7 - 8 year range. 2) Absorption test Table 3

[00199] The weight swelling of PP-H 100 is very low even at 95°C 3) Tensile test Table 4


[00200] Reference materials are not aged. Changes in mechanical properties after 20 weeks under different conditions are all minor. 4) Microscopic investigation
[00201] The results are shown in figure 4.
[00202] Figure 4a is an unexposed reference sample. The left side is an LM image of a microtomized cross section. The right side is an SEM image of the surface.
[00203] Figure 4b is PP-H-100 plates that have been exposed for 20 weeks in 30% aqueous MEA solution at 95°C. The left side is an LM image of a microtomized cross section. The right side is an SEM image of the surface.
[00204] No significant differences were observed in morphology or surface after 20 weeks of exposure. The structures seen on the surface (SEM images) are caused by artifacts (fingerprints) and varying amounts of scratches on the mold have given some variations in the surface copy. No micro-scratch was observed. 5) DSC
[00205] The results are shown in the table below and in the graph in Figure 5 where Figure 5a shows the DSC curve of reference material, Figure 5b shows DSC curves of reference material compared to samples exposed by 1, 2, 3 and 8 weeks and Figure 5c shows DSC curves from samples exposed for 8 weeks and 20 weeks. Table 6


[00206] DSC shows no significant change in β-phase due to exposure to 95°C, 20 weeks. Test of BE60-7032 plates containing IRGANOX 1010, IRGANOX 1330, DSTDP and SHT
[00207] Unaged plates comprised the following composition as determined by the method described: IRGANOX 1010 2880 ppm p AO 1330 4250 ppm p DSTDP 4900 ppm p SHT 1000 ppm p 1) Determination of the amount of AO present in aged samples
[00208] The amount of antioxidants present in plates aged in amine solutions at different temperatures (p ppm) is shown in the table below. Aged in used aqueous solution of AMP and AEP (p ppm) Table 7

Aged in a new 30% aqueous solution of MEA (p ppm) Table 8

[00209] The test was performed on two different amines, ie, 30% aqueous solution of MEA and aqueous solution of a mixture of AEP and AMP, which were used for carbon capture for several months. The rationale for solvent selection is to clarify whether there is a significant difference between different amines and also to investigate whether amine degradation products have a detrimental effect on polypropylene.
[00210] The results show that IRGANOX 1330 is not significantly depleted after exposure to either of the two solutions.
[00211] A lifetime prediction based on the results of depletion of IRGANOX 1010+A01330 from BE60-7032 plates (8 mm thick) stored in fresh 30% aqueous MEA solution and used aqueous AMP and AEP 80 solution °C and 95°C was also carried out.
[00212] The logarithmic relationship between AO concentration (IRGANOX 1010+A01330) in BE60-7032 plates and exposure time in both new 30% aqueous MEA solution and used aqueous AMP and AEP solution at 80°C and 95 °C is shown in Figures 6a and 6b below.
[00213] Using the equations as shown in the figures the time until the concentration of IRGANOX 1010 + IRGANOX 1330 = 1 ppm can be calculated, and the results are shown in comparison with the commercially available PP-H 100 results in the table below. Table 9


These results show a more than 5-fold extended time to AO = 1ppm by adding IRGANOX 1330 and SHT at both 95°C and 80°C.
[00215] Placing the results on an Arrhenius graph (Figure 6c) the time to AO = 1 ppm at 75°C was calculated to be about 650 weeks (12.5 years) for both the new MEA and the used amine solution .
[00216] Taking all factors into consideration a shelf life of 8mm thick BE60-7032 with IRGANOX 1330 and SHT, continuously exposed by aqueous amine solution (new or used) at 75 °C, on one side, was predicted as being >15 years, more likely close to 20 years.
[00217] Test on double plates
[00218] All the tests described above were carried out on 8 mm thick plates in 30% aqueous solution of MEA, i.e. exposure to amine on both sides. To better simulate real-world conditions where amine exposure only occurs on one side, two 8mm plates were welded together giving a total thickness of 16mm. Both 8 mm and 16 mm plates were aged for 15 weeks in 30% aqueous MEA solution at 80 °C and 95 °C, and the remaining antioxidant content analyzed.
[00219] Antioxidants (ppm) on plaques before aging: Table 10


[00220] Antioxidants (ppm) on plates aged in new MEA at 30% (ppm) for 15 weeks: Table 11
single plates
[00221] The time to concentration of IRGANOX 1010 + IRGANOX 1330 = 1 ppm was estimated based on results up to 15 weeks of aging: Table 12
AO depletion as a function of time is shown in Figure 7a.
These results show very little reduction in concentrations of IRGANOX 1330 both at 80 °C and 95 °C. There can be different reasons for this: a) The very good hydrolytic stability of IRGANOX 1330 b) IRGANOX 1010 and the hydrolyzed IRGANOX 1010 can react faster than IRGANOX 1330 with peroxy-radicals, stopping polymer degradation. For this reason, the molecules of IRGANOX 1330 are “protected” as much as the molecules of active IRGANOX 1010 and hydrolyzed IRGANOX 1010 exist in the polymer. Lifetime prediction at 65 °C
[00223] Placing these results on an Arrhenius plot, as shown in figure 7b, a shelf life of 8mm thick BE60-7032 liner with IRGANOX 1330, continuously exposed by 30% MEA solution at 65°C can be estimated.
[00224] This estimate shows a shelf life of 1300 weeks (25 years) at 65 °C with amine exposure on both sides. Using the change in concentration of IRGANOX 1010 + IRGANOX 1330 for the shelf life prediction, predictions made after short storage times (eg 15 weeks) will be mainly influenced by hydrolysis of IRGANOX 1010. The shelf life predictions are therefore underestimated.
[00225] Taking all factors into consideration a shelf life of BE60-7032 8 mm thick with IRGANOX 1330, continuously exposed by 30% MEA solution (new or used) at 65°C, on one side, was predicted as being >25 years, most likely >30 years as well. 2) New Amine Absorption Test Table 13
New amine - double plate, soldered samples Table 14
Used amine Table 15

[00226] The weight swelling of PP-H 100 is very low even at 95 °C both in used and new amine. 3) Tensile strength Amine new Table 17
Used amine Table 18

[00227] The reference materials are all unaged. Changes in mechanical properties after 8 and 12 weeks under different conditions are all minor. 4) Microscopic investigation
[00228] The results are shown in figure 8.
[00229] Figure 8a is a reference sample. The left side is an LM image of a microtomized cross section. The right side is an SEM image of the surface.
[00230] Figure 8b is plates of BE60-7032 that have been exposed for 12 weeks in 30% MEA in aqueous solution at 95 °C (new MEA). The left side is an LM image of a microtomized cross section. The right side is an SEM image of the surface.
[00231] Figure 8c is plates of BE60-7032 that were exposed for 12 weeks in aqueous amine solution at 95°C (using AMP/AEP mixture). The left side is an LM image of a microtomized cross section. The right side is an SEM image of the surface.
[00232] No significant differences were observed in morphology and surface after 12 weeks of exposure. The structures seen on the surface (SEM images) are caused by artifacts (fingerprints) and varying amounts of scratches on the mold giving some variations in the surface copy. No micro-scratch was observed in any of the inspected samples. DSC
[00233] The results are shown in the tables below and in the graphs in Figure 9 where Figure 9a shows the DSC curve of reference material, Figure 9b shows the DSC curve of reference material compared to samples exposed to the amine fresh for 3, 8 and 12 weeks and Figure 9c shows the DSC curves of reference material compared to samples exposed to amine used for 8 and 12 weeks. New Amine Table 19
Used amine Table 20

Aging at 130 °C after aging in amine solution at 95 °C Sample P1 and P2
[00234] The compositions of Sample P1 and Sample P2 used in the test are shown in the table below. Both samples are based on the same polymer. Table 21, below, shows the antioxidant composition as analyzed before aging, whereas the SHT concentration is the concentration as it was added and was not analyzed. Table 21

[00235] Initially and prior to aging in this study, Samples P1 and P2 were aged in a solution of piperazine/AMP (0.45 M piperazine + 0.9 M AMP) (pH — 12.5) at 95 °C , P1 for 36 weeks and P2 for 52 weeks. Measurements of added antioxidants are illustrated in Figures 10a and 10b for IRGANOX 1010 and AO1020 in combination with IRGANOX 1330, respectively. No measurable IRGANOX 1010 was found in P1 or P2 after 32 weeks, whereas 65% of IRGANOX 1330 remains in Sample P2 after 1 year (52 weeks) of aging.
[00236] Although no IRGANOX 1010 remained in Sample P1 the mechanical properties after 36 weeks of aging are almost unchanged. Also for Sample P2 the mechanical properties are almost unchanged after 52 weeks of aging.
[00237] These aged pre-samples were placed in an oven at 130 °C, with circulated air (ie higher temperature and easier access to oxygen compared to aging in piperazine + AMP solution) and visually inspected until 14 weeks of aging at 130 °C, then samples were tested for mechanical stress. B) Sample P5 and P10
[00238] The compositions of Sample P5 and Sample P10 are shown in table 22. Both compositions are based on the same polymer. Table 22, below, shows the antioxidant composition as analyzed prior to aging, whereas the SHT concentration is the concentration as it was added and was not analyzed. Table 22


[00239] Initially, Samples P5 and P10 were aged in a solution of piperazine/AMP (0.45 M piperazine + 0.9 M AMP) (pH - 12.5) at 95 °C, for 12 weeks. The remaining antioxidants are as shown in Table 23, below. Table 23

[00240] These aged pre-samples were placed in an oven at 130 °C, with circulated air (ie higher temperature and easier access to oxygen compared to aging in piperazine + AMP solution) and visually inspected until 14 weeks of aging at 130 °C, then samples were tested for mechanical stress. The effect of piperazine + AMP on antioxidants and polymer
[00241] 1mm-thick samples of Sample P3 (PP polymer with no added antioxidants) were aged in air, water and a solution of piperazine/AMP (0.45M piperazine + 0.9M AMP) (pH - 12.5) at 95 °C until eventually crack failure, and samples aged for 32 weeks in piperazine + extra AMP aged at 130 °C until brittle. Samples were visually inspected and mixed 180° each week until failure. Tensile Test - Per ISO 527-2 Zwick Z010 Instrument with Macro Strain Gauge Specimen Type Multi-Purpose Type 1B, Molded and Compression Milled, Thickness 8 mm Test Conditions Test Speed 50 mm/min. Modulus of tension 1 mm/min Definitions Modulus of tension, MPa - (the modulus of elasticity in tension) - the slope of a secant line between 0.05% and 0.25% strength on a stress-resistance curve. Tensile effort/strength in yield, MPa / % - tensile effort/strength corresponding to the yield point (an increase in strength does not result in an increase in effort). Tensile strength at breaking, % - tensile strength corresponding to the breaking point Tensile strength at breaking, MPa - tensile strength corresponding to the breaking point Results and discussions
[00242] Table 24, below, shows the time until the first visual sign of surface degradation of samples P1, P2, P5 and P10 given in days at 130 °C aging in air after the samples were pre-aged in the mixture of piperazine/AMP solution mentioned above (0.45 M piperazine + 0.9 M AMP)(pH - 12.5) for the time periods identified above. Table 24

[00243] The first sign of surface degradation of Sample P1 after 72 days is shown in Figure 11, along with Sample P2 aged for 86 days, and Sample 3 (PP without added antioxidant, pre-aged at 32 weeks in solution of piperazine/AMP (0.45 M piperazine + 0.9 M AMP)(pH - 12.5) and first sign of surface degradation after 12 days at 130 °C, and fully cracked after 24 days at 130 °C C, as shown in figure 11.
[00244] Figure 25, below, shows the change in mechanical properties of Samples P2, P1, P5 and P10 as a function of Sample P1 and P2. Table 25


[00245] The mechanical properties as shown in Table 25 show little variations during the aging of Effort in Yield, Strength in Yield and Stress in Breaking of both P1 and P2. The tensile modulus and breaking strength as a function of aging are seen as shown in figure 12.
[00246] The reduction in Tensile Modulus and Breakdown Strength of Sample P1 clearly shows that polymer degradation was initiated and most likely resulted in a fully cracked polymer after a few extra weeks of aging at 130 °C as seen for Sample P3 with no added antioxidant (Figure 2). In literature often 50% reduction in Crack Strength is used as failure criteria for polymer aging. P1 is reduced by 60% after 36 weeks in piperazine + AMP at 95 °C + 4 weeks at 130 °C. The same properties in P2, after longer aging time, are changed less, most likely due to the much better stabilization system in P2.
[00247] In figure 13 the fracture surfaces of Sample P1 after 36 weeks in piperazine + AMP at 95 °C + 14 weeks at 130 °C as well as Sample P2 after 52 weeks in piperazine + AMO at 95 °C + 14 weeks at 130 °C, after tensile test to breakage. The figure shows a partially cracked fracture of P1 and some polymer degraded close to the surface (upper left P1 a), whereas Sample 2 showed a more ductile behavior and no sign of surface degradation was seen b) Samples P5 and P10
[00248] The only difference in composition between Sample P5 and P10 is the 1000 ppm SHT in Sample P5. The results in Tables 23 - 25 show that the remaining concentration of IRGANOX 1330 after 12 weeks of aging in piperazine + AMP is the same and an extra 14 weeks of aging at 130 °C shows no surface degradation or change in mechanical properties, i.e. is, the aging time is too short to be distinguished between these two Samples. c) The effect of piperazine + AMP on antioxidants and polymer
[00249] The results after aging 1mm thick unstabilized PP (Sample P3) under different conditions are shown in Table 6. Table 26
Table 26, Time to first surface degradation and P3 brittleness in different media
[00250] The results show that the time to first sign of surface degradation (yellow dots) was almost the same for PP not stabilized at 95 °C both in water and air. However, the time to crack failure was faster in air than in water.
[00251] The results in Table 6 also show that the amine solution comprising piperazine + AMP has a stabilizing effect on polypropylene with no sign of surface degradation after 32 weeks in piperazine/AMP solution (0.45 M piperazine + 0 .9 M AMP)(pH = 12.5) at 95°C. However, after removing Sample P3 from the piperazine + AMP at 130°C in air the sample failed after a few days (12 days).
[00252] The results indicate that piperazine + AMP has a negative effect on the depletion of the antioxidant IRGANOX 1010 (as seen for Sample P1) compared to the depletion of IRGANOX 1010 in water (both pH 4.5, pH 7 and pH 12.5). The reason may be that the amine composition comprising piperazine + AMP slightly swells the polymer and may also bring some water into the polymer, and the IRGANOX 1010 molecule may be hydrolyzed within the polymer. For PP polymers stored in water, hydrolysis of IRGANOX 1010 is reported to occur at the surface, ie less hydrolyzed AO 1010 and slower depletion of IRGANOX 1010. This again shows that it is important to choose the right polypropylene stabilization. At the same time all test results of Sample P2 show that the P2 antioxidant system gives very good long-lasting properties in amine solutions with estimated service life in piperazine + AMP at 95 °C for 20 years, and with certainty > 30 years at 80 °C. Conclusions - The first sign of polymer degradation from Sample P1 is seen after 36 weeks in piperazine + AMP at 95 °C plus 72 days at 130 °C in air. - No sign of polymer degradation from Sample P2 after 52 weeks in piperazine + AMP at 95 °C plus 96 days at 130 °C in air. - Time at 130 °C (96 days) was too short to distinguish between Sample P5 and P10 to see the real effect of SHT - Piperazine + AMP has a negative effect on depletion of the antioxidant IRGANOX 1010 - Piperazine + AMP has a stabilizing (antioxidant) effect on polypropylene Antioxidant depletion as a function of time in aqueous solutions
[00253] The results obtained for the depletion of antioxidant in test specimens P1 and P3 as indicated above, as a function of time in different aqueous solutions are given in Figures 14 and 15, showing the depletion of IRGANOX 1010 and IRGANOX 1330, respectively , in water, and in aqueous solutions of MEA, AMP + AEP, AMP + piperazine, NaOH and H2SO4. All tests were performed at 95°C in the indicated solution. The results are taken both from the above examples and from the separate tests carried out as described above, and the results are collected in the figures mentioned.
[00254] It is known that polyolefin is not exposed to thermal degradation resulting in loss of mechanical properties as much as phenolic antioxidants such as IRGANOX 1010 or IRGANOX 1330 are present in the polymer blend. Depletion of antioxidants is thus an indication of unwanted loss of properties required of polymers.
[00255] It can be seen from Figures 14 and 15 that IRGANOX 1010 is depleted more rapidly from polyolefin by the tested amine solutions than by water or acidic or basic water, even if the pH of the basic water is the same as for the amine solutions. All IRGANOX 1010 is polymer depleted after 15 weeks, whereas IRGANOX 1330 remains substantially unchanged for the same period.
[00256] The finding that IRGANOX 1330 remains substantially unchanged for 15 weeks when soaked in amine solutions at 95°C indicates that the antioxidant remains in the polypropylene for a sufficiently long period under running conditions in a plant to capture CO2 . This result is not expected from the findings in the paper identified above by Müller et al, which reports on a much faster depletion of IRGANOX 1330 from the polymers tested in them.
[00257] Possible explanations for the unexpectedly long time before total depletion of IRGANOX 1330 from the polypropylene tested could be the specific composition of additives in the polymer tested, interaction with SHT, or differences in the polypropylene polymer. Additional life tests that can provide answers to these questions are being carried out.

权利要求:
Claims (9)
[0001]
1. Method for capturing an acid gas (eg CO2) in an exhaust gas characterized by comprising: placing said exhaust gas in contact with an aqueous amine absorbent in an absorption column, wherein at least a part of the said absorption column comprises polypropylene, wherein the polypropylene composition comprises a hydrolytically stable antioxidant stable in amine solutions, of formula
[0002]
2. Method according to claim 1, characterized in that the polypropylene composition further comprises a heat stable antioxidant of formula (IIIb)
[0003]
3. Method according to claim 2, characterized in that said heat stable antioxidant is
[0004]
4. Method according to any one of claims 1 to 3, characterized in that the polypropylene composition further comprises one or more of a phosphonite or organic phosphite antioxidant, and/or a sulfoether antioxidant.
[0005]
5. Method according to any one of claims 1 to 4, characterized in that the propylene polymer comprises a beta-crystalline phase
[0006]
6. Method according to any one of claims 1 to 5, characterized in that the polypropylene composition further comprises synthetic hydrotalcite.
[0007]
7. Method according to any one of claims 1 to 6, characterized in that said absorption column is constructed of concrete, metal or composite material.
[0008]
8. Method according to any one of claims 1 to 7, characterized in that the surface of the absorption column expected to be exposed to the aqueous absorbent of amine, amine vapor and/or steam is coated with said polypropylene composition.
[0009]
9. Method according to any one of claims 1 to 8, characterized in that the surface of the absorption column expected to be exposed to the aqueous amine solution, its vapor or steam is a lining comprising said composition of polypropylene which is fixed to the surface of the absorption column.

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公开号 | 公开日

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DK2729232T3|2018-05-28|

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EA201490190A1|2014-06-30|

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EP2729232A1|2014-05-14|

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CN103796732B|2017-03-15|

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EA026720B1|2017-05-31|

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WO2013004797A1|2013-01-10|

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NO336115B1|2015-05-18|

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AU2012280258B2|2017-05-18|

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JP6180411B2|2017-08-16|

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AU2012280258A1|2013-01-10|

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CN103796732A|2014-05-14|

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EP2729232B1|2018-02-14|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-01| B25C| Requirement related to requested transfer of rights|Owner name: AKER ENGINEERING AND TECHNOLOGY AS (NO) Free format text: A FIM DE ATENDER A(S) TRANSFERENCIA(S), REQUERIDA(S) ATRAVES DA PETICAO NO 870190054411 DE 13/06/2019, E NECESSARIO APRESENTAR PROCURACAO ATUALIZADA ONDE CONSTE O NOVO NOME DA TITULAR E A NOMEACAO DO PROCURADOR DEFINITIVO. |

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2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2019-10-15| B25F| Entry of change of name and/or headquarter and transfer of application, patent and certif. of addition of invention: change of name on requirement|Owner name: AKER ENGINEERING AND TECHNOLOGY AS (NO) Free format text: A FIM DE ATENDER A(S) ALTERACAO(OES) REQUERIDA(S) ATRAVES DA PETICAO NO 870190054586 DE13/06/2019, E NECESSARIO APRESENTAR PROCURACAO ATUALIZADA ONDE CONSTE O NOVO NOME DA TITULAR EA NOMEACAO DO PROCURADOR DEFINITIVO. |

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2019-12-10| B25L| Entry of change of name and/or headquarter and transfer of application, patent and certificate of addition of invention: publication cancelled|Owner name: AKER ENGINEERING AND TECHNOLOGY AS (NO) Free format text: ANULADA A PUBLICACAO CODIGO 25.6 NA RPI NO 2545 DE 15/10/2019 POR TER SIDO INDEVIDA. |

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2019-12-24| B25L| Entry of change of name and/or headquarter and transfer of application, patent and certificate of addition of invention: publication cancelled|Owner name: AKER ENGINEERING AND TECHNOLOGY AS (NO) Free format text: ANULADA A PUBLICACAO CODIGO 25.3 NA RPI NO 2543 DE 01/10/2019 POR TER SIDO INDEVIDA. |

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2020-01-21| B25A| Requested transfer of rights approved|Owner name: AKER SUBSEA AS (NO) |

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2020-02-11| B25D| Requested change of name of applicant approved|Owner name: AKER SOLUTIONS AS (NO) |

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2020-12-29| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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NO20110971|2011-07-05|

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PCT/EP2012/063185|WO2013004797A1|2011-07-05|2012-07-05|Construction element for co2 capture|

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