IMPROVED MATERIALS FOR DIRECT AIR CAPTURE AND USES THEREOF

Abstract

A method for separating gaseous carbon dioxide from air is proposed by cyclic adsorption/desorption using a sorbent. The method includes the following sequential and in this sequence repeating steps: (a) contacting air with the sorbent to allow gaseous carbon dioxide to adsorb on the sorbent under ambient atmospheric pressure and temperature conditions; (b) isolating the sorbent from the flow-through; (c) inducing an increase of the temperature of the sorbent; (d) extracting the desorbed gaseous carbon dioxide from the unit and separating gaseous carbon dioxide from steam/water; and (e) bringing the sorbent to ambient atmospheric temperature and pressure conditions. The sorbent is a water retaining and/or porous support which before use in the cyclic process has been impregnated or wetted with a solution of a secondary amine compound and the sorbent is loaded by said secondary amine compound by at least 5% by weight.

Claims

1. A method for separating gaseous carbon dioxide from a gas mixture, containing said gaseous carbon dioxide as well as further gases different from gaseous carbon dioxide, by cyclic adsorption/desorption using a sorbent material adsorbing said gaseous carbon dioxide in a unit, wherein the method comprises at least the following sequential and in this sequence repeating steps (a)-(e): (a) contacting said gas mixture with the sorbent material to allow at least said gaseous carbon dioxide to adsorb on the sorbent material by flow-through through said unit under ambient atmospheric pressure conditions and ambient atmospheric temperature conditions in an adsorption step; (b) isolating said sorbent material with adsorbed carbon dioxide in said unit from said flow-through while maintaining the temperature in the sorbent; (c) inducing an increase of the temperature of the sorbent material starting the desorption of CO2; (d) extracting at least the desorbed gaseous carbon dioxide from the unit and separating gaseous carbon dioxide from steam and/or water by condensation in or downstream of the unit; (e) bringing the sorbent material to ambient atmospheric temperature and pressure conditions; wherein said sorbent material is based on or consists of an inorganic or organic, non-polymeric or polymeric support material which before use in the cyclic process has been impregnated or wetted with a liquid solution of a secondary cycloaliphatic or aromatic amine compound, and wherein said support material is loaded by said secondary cycloaliphatic or aromatic amine compound by at least 5% by weight, calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material.

2. Method according to claim 1, wherein the secondary cycloaliphatic or aromatic amine compound is a secondary cycloaliphatic amine compound having 3-10, ring atoms of which at least one, or at least two are amino atoms.

3. Method according to claim 1, wherein said support material, is loaded by said secondary cycloaliphatic or aromatic amine compound by at least 7% by weighty calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material, and/or wherein the sorbent material is at least partially dried after the impregnation or wetting.

4. Method according to claim 1, wherein in the process said sorbent material has a water content of more than 10% by weight, calculated as percentage of mass of water in g relative to 100 g of said dry sorbent material.

5. Method according to claim 1, wherein the secondary cycloaliphatic amine compound for impregnation or wetting is dissolved in a polar solvent, and/or a wherein the concentration of the secondary cycloaliphatic or aromatic amine compound, in the liquid solution for impregnation or wetting is in the range of at least 5% or 20-80% by weight, and/or wherein impregnation or wetting takes place at a liquid solution temperature in the range of 20-60 C.

6. Method according to claim 1, wherein said solid inorganic or organic, non-polymeric or polymeric porous support material is at least one of activated carbon, cellulose, including nano cellulose and nanocrystalline cellulose, cotton.

7. Method according to claim 6, wherein said support material is loaded by said secondary cycloaliphatic or aromatic amine compound by at least 10% by weight, calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material.

8. Method according to claim 1, wherein said solid inorganic or organic, non-polymeric or polymeric porous support material is activated carbon, which is functionalised, either before, during or after impregnation or wetting with said secondary cycloaliphatic or aromatic amine compound, with at least one alkali carbonate salt selected from the group consisting of: K2CO3, Li2CO3, Na2CO3 as well as mixed salts thereof.

9. Method according to claim 8, wherein said support material is loaded by said alkali carbonate salt by at least 10% by weight calculated as dry weight of said impregnated alkali carbonate salt relative to the total dry weight of said sorbent material, and wherein said support material is loaded by said secondary cycloaliphatic or aromatic amine compound by at least 7% by weight, calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material.

10. Method according to claim 1, wherein said step (c) involves, exclusively or additionally, injecting a stream of saturated or superheated steam by flow-through through said unit and thereby inducing an increase of the temperature of the sorbent material, starting the desorption of CO2.

11. Method according to claim 1, wherein downstream of said unit, said secondary cycloaliphatic or aromatic amine compound is recovered and separated from steam and/or water or concentrated in water.

12. Method according to claim 1, wherein said support material has a water retention capacity>0.1 ml/g, and/or wherein said support material, wetting/impregnation loaded by said secondary cycloaliphatic or aromatic amine compound by in the range of 5-20% by weight has a T-plot micro-porosity volume of at least 0.1 ml/g, and/or a T-plot micro-porosity area of at least 200 m2/g, and/or a total porosity of at least 0.4 ml/g, and/or a specific BET surface area of at least 200 m2/g, and/or wherein said support material, before wetting/impregnation has a T-plot micro-porosity of at least 0.3 ml/g, and/or a total porosity of at least 0.4 ml/g, and/or a specific BET surface area of at least 1000 m2/g.

13. Method according to claim 1, wherein said sorbent material is biomass-based.

14. Method according to claim 1, wherein under high relative humidity conditions of more than 80% relative humidity at least every 20 cycles, or at least every 10 cycles, or at least every 5 cycles, there is an additional step of drying the sorbent material.

15. Method of manufacturing a sorbent material suitable and adapted for use in a method according to claim 1, wherein an inorganic or organic, non-polymeric or polymeric support material is impregnated or wetted, preferably by immersion or sprinkling, with a liquid solution of a secondary cycloaliphatic or aromatic amine compound, and is subsequently dried at least partially, to result in a material loaded by said secondary cycloaliphatic or aromatic amine compound by at least 5% by weight, calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material.

16. Method according to claim 1, wherein it is for separating gaseous carbon dioxide from from at least one of ambient atmospheric air, flue gas and biogas, containing said gaseous carbon dioxide as well as further gases different from gaseous carbon dioxide,

17. Method according to claim 1, wherein step (c) involves inducing an increase of the temperature of the sorbent material to a temperature between 60 and 110 C., starting the desorption of CO2

18. Method according to claim 1, wherein the secondary cycloaliphatic or aromatic amine compound is a secondary cycloaliphatic amine compound having 5-6 ring atoms of which at least one, or at least two are amino atoms.

19. Method according to claim 1, wherein the secondary cycloaliphatic or aromatic amine compound is selected from the group consisting of: aziridine, diaziridine, azetidine, 1,2 or 1,3 diazetidine, pyrrolidine, diazolidine, triazolidine, piperidine, 1,2 or 1,3 diazinane, piperazine, triazinane, tetrazinane, azepane, azocane, azonane, and mixtures thereof

20. Method according to claim 1, wherein the secondary cycloaliphatic or aromatic amine compound is selected as piperazine.

21. Method according to claim 1, wherein said support material, in the form of a solid water-retaining, porous support material, is loaded by said secondary cycloaliphatic or aromatic amine compound by in the range of 7-65%, or in the range of 9-40% by weight or 10-30% by weight, in each case calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material.

22. Method according to claim 21, wherein the secondary cycloaliphatic or aromatic amine compound is at least partially dried after the impregnation or wetting.

23. Method according to claim 1, wherein in the process said sorbent material has a water content of more than 40% by weight, or in the range of 25-150%, in the range of 50-110% or in the range of 60-80% by weight, in each case calculated as percentage of mass of watering relative to 100 g of said dry sorbent material.

24. Method according to claim 1, wherein the secondary cycloaliphatic amine compound for impregnation or wetting is dissolved in a polar solvent, in the form of water, methanol, ethylene glycol, or a mixture thereof, and/or a wherein the concentration of the secondary cycloaliphatic or aromatic amine compound, selected as piperazine, in the liquid solution for impregnation or wetting is in the range of 25-50% or 25-% by weight, and/or wherein impregnation or wetting takes place at a liquid solution temperature in the range of 40-50 C.

25. Method according to claim 1, wherein said solid inorganic or organic, non-polymeric or polymeric porous support material is at least one of activated carbon, cellulose, including nano cellulose and nanocrystalline cellulose, cotton, in at least one of particulate form, monolithic form and loose, woven or nonwoven fibre form.

26. Method according to claim 6, wherein said support material is loaded by said secondary cycloaliphatic or aromatic amine compound by in the range of 15-65%, or in the range of 20-40% by weight or 25-30% by weight, in each case calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material.

27. Method according to claim 1, wherein said solid inorganic or organic, non-polymeric or polymeric porous support material is activated carbon, in particulate, monolithic and loose, woven or nonwoven fibre form, which is functionalised before or during impregnation or wetting, with at least one alkali carbonate salt selected from the group consisting of: K2CO3, Li2CO3, Na2CO3 as well as mixed salts thereof, wherein the solid inorganic or organic, non-polymeric or polymeric porous support material is impregnated with a mixture of at least two different alkali carbonate salts selected from the group consisting of: K2CO3, Li2CO3, Na2CO3, and wherein an alkali carbonate salt with the smallest weight proportion in the mixture is present in an amount of at least 5 weight % with respect to the total of the impregnating mixture of at least two alkali carbonate salts, and/or wherein the impregnating mixture of mixture of at least two alkali carbonate salts comprises at least Na2CO3, or said mixture comprising or consisting of K2CO3 as well as Na2CO3, in a weight ratio of K2CO3 to Na2CO3 in the range of 95:5-5:95, or in the range of 90:10-10:90, or in the range of 40:60-95:5.

28. Method according to claim 8, wherein said support material is loaded by said alkali carbonate salt by at least 15% by weight, or at least 20% by weight, in the range of 20-35%, or 22-28% by weight, in each case calculated as dry weight of said impregnated alkali carbonate salt relative to the total dry weight of said sorbent material, and wherein said support material is loaded by said secondary cycloaliphatic or aromatic amine compound by in the range of 7-20% by weight, or 9-15% by weight, in each case calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material.

29. Method according to claim 1, wherein said step (c) involves, exclusively or additionally, injecting a stream of saturated or superheated steam by flow-through through said unit and thereby inducing an increase of the temperature of the sorbent material, to a temperature between 60 and 110 C., starting the desorption of CO2.

30. Method according to claim 1, wherein downstream of said unit, during or downstream of said condensation separating gaseous carbon dioxide from water and/or steam injected in step (c), said secondary cycloaliphatic or aromatic amine compound is recovered and separated from steam and/or water or concentrated in water, and wherein said recovered secondary cycloaliphatic or aromatic amine compound is used again for impregnation or wetting of said sorbent material.

31. Method according to claim 31, wherein said recovered secondary cycloaliphatic or aromatic amine compound is used for re-impregnation or re-wetting of the sorbent material in said unit by sprinkling a solution thereof between or during one of steps (a)-(e), or after step (d) or during or after (e).

32. Method according to claim 1, wherein said support material has a water retention capacity>0.5 ml/g, or >1 ml/g, or >2 ml/g, caused by internal porosity, capillary forces, surface adhesion or a combination thereof and/or wherein said support material, in the form of active carbon, after wetting/impregnation loaded by said secondary cycloaliphatic or aromatic amine compound by in the range of 5-20% by weight has a T-plot micro-porosity volume of at least 0.2 ml/g, and/or a T-plot micro-porosity area of at least 300 m2/g, and/or a total porosity of at least 0.5 ml/g, and/or a specific BET surface area of at least 400 m2/g or 500-900 m2/g. and/or wherein said support material, in the form of active carbon, before wetting/impregnation has a T-plot micro-porosity of at least 0.6 ml/g, and/or a total porosity of at least 1 ml/g, or of at least 1.5 ml/g, and/or a specific BET surface area of at least 1500 m2/g or at least 1800 m2/g.

33. Method according to claim 1, wherein said sorbent material is biomass-based, with high nitrogen content, and wherein said material is carbonised prior to being impregnated or wetted with said amine solution.

34. Method according to claim 1, wherein under high relative humidity conditions of more than 80% relative humidity at least every 20 cycles, or at least every 10 cycles, or at least every 5 cycles, there is an additional step of drying the sorbent material, by at least one of evacuation, introducing hot dry air into the unit and electrical internal heating.

35. Method of manufacturing a sorbent material according to claim 15, wherein said inorganic or organic, non-polymeric or polymeric, water-retaining or porous support material is impregnated or wetted, by immersion or sprinkling, with a liquid solution of a secondary cycloaliphatic or aromatic amine compound, and is subsequently dried at least partially, to result in a material loaded by said secondary cycloaliphatic or aromatic amine compound by at least 5% by weight, calculated as dry weight of said impregnated or wetted secondary cycloaliphatic or aromatic amine compound relative to the total dry weight of said sorbent material, wherein the secondary cycloaliphatic amine compound for impregnation or wetting is dissolved in a polar solvent, including water, methanol, ethylene glycol, or a mixture thereof, and/or wherein the concentration of the secondary cycloaliphatic or aromatic amine compound in the liquid solution for impregnation or wetting is in the range of at least 5% or 25-80% by weight, or in the range of 25-40% or 25-40% by weight, and/or wherein impregnation or wetting takes place at a liquid solution temperature in the range of 20-60 C., or in the range of 40-50 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Preferred embodiments of the invention are described in the following with reference to the drawings, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same. In the drawings,

[0073] FIG. 1 shows a schematic representation of a direct air capture unit;

[0074] FIG. 2 shows a schematic representation of thermo-reactor used in the first experiments (desorption mode);

[0075] FIG. 3 shows cyclic test data for BBOS-1A (a) and BBOS-1B (b) sorbent in the first experiments;

[0076] FIG. 4 shows cyclic test data for BBOS-1B sorbent in the second experiments;

[0077] FIG. 5 shows CO2 flow during the desorption step (example for cycle 11 at % RH=80);

[0078] FIG. 6 shows CO2 capacity as function of the moisture content of Active Carbon materials;

[0079] FIG. 7 shows the evolution of the moisture content and the capacity;

[0080] FIG. 8 shows the evolution of the moisture content and the capacity;

DESCRIPTION OF PREFERRED EMBODIMENTS

[0081] FIG. 1 shows, in a schematic representation, a direct air capture unit 8. There is provided a container having a wall 7, and in this container the sorbent material 3 is contained. Inflow 1 of ambient air enters the container, either by a corresponding openings or by air permeable wall structures, and exits downstream of the sorbent as outflow 2. There is provided an inlet for steam 4, which can be either the same inlet as for the air or a separate inlet. There is further provided an outlet for extraction, which again can either be a different outlet than the ones for air or the same. Downstream of the outlet 5 there is provided a separator 6, for example in the form comprising a vacuum unit.

[0082] Activated carbon impregnated with alkali carbonate and piperazine:

[0083] Potassium carbonate based active carbon (AC) sorbent despite its ability to be used for CO2 capture from ambient air under normal conditions (RH % below <80%) may show a certain deactivation trend when used at higher RH. The deactivation is assumed to be mainly related to high water adsorption during adsorption step from humid air. To improve the K2CO3/AC sorbent performance under such severe conditions (RH %>80) piperazine (PZ) is further applied as a promoting component in the sorbent composition to improve kinetics for CO2 adsorption and keep in this way sorbent capacity at the desired level.

[0084] Sorbent Preparation:

[0085] Two sorbent compositions were prepared: BBOS-1A (GLC-10*32-36% K2CO3/9% PZ) and BBOS-1B (GLC-10*32-25% K2CO3/15% PZ).

[0086] The porous activated support in this case is granular activated carbon having a standard particle size of 10-30 (mesh) as available under the product designation GLC-10*32 from Kuraray (JP) (see below for further details and porosity information). The support material is impregnated with 36% and 25% by weight (dry weight), respectively, of K2CO3 and with 9% and 15% by dry weight, respectively, with piperazine.

[0087] The required amount of K2CO3 (36 g and 25 g) and PZ (9 and 15 g) were dissolved in 110 g of demineralised water under heating up to 40 C. to prepare BBOS-1A and BBOS-1B sorbents, respectively.

[0088] The obtained solution was thoroughly mixed with 60 g of the porous activated support material to ensure liquid filling the pore system of the support.

[0089] The sample was dried in air at 105 C. in a fan of oven to remove water. Before tests the water content in the samples was measured.

[0090] As effect of the impregnation the accessible porosity gets reduced and is determined by nitrogen adsorption to a T-plot micro-porosity of 0.225 ml/g, a total porosity of 0.63 ml/g and a specific surface area of 742 m2/g (please see below for experimental details).

[0091] First Experimental Procedure:

[0092] CO2 capture from ambient air has been performed in a thermo-reactor with double walls to prevent heat exchange between the sorbent and environment during the desorption step (FIG. 2). About 100 g of the sorbent was placed into the reactor. CO2 adsorption tests were performed with ambient air (led through a moisturizer to adjust the airflow to 75-85% RH).

[0093] Adsorption time 5h was applied due to limitations in the air-pump capacity. The exact experimental conditions are shown in the corresponding figures with the experimental data. CO2 sorbent capacity was measured following CO2 concentration at the reactor outlet during the adsorption experiment.

[0094] Results of First Experimental Procedure:

[0095] To determine the sorbent performance during the cyclic tests ambient air flow with 80% RH was used.

[0096] Data for CO2 capacity and water content in the sorbents tested are presented in FIG. 3. CO2 adsorption capacity for BBOS-1A is stable within the first three cycles0.6-0.65 mmol CO2/g sorbent, see FIG. 3a. For the next three cycles the capacity decreases and is equal to 0.38 mmol CO2/g sorbent for the cycle 6 adsorption. The same time we measured increase in water content in the sorbent with each adsorption cycle. When an intermediate drying step between adsorption and desorption is introduced, the water content in the sorbent decreases to initial 60% and the sorbent capacity is restored. For cycle 7, performed after drying step, the capacity goes up to its original value0.63 mmol CO2/g sorbent. Further testing, cycle 8 shows the similar tendency as for cycle 4 CO2 sorbent capacity decreases in line with increase in water content in the sorbent. From these data we can conclude that to keep high sorption capacity for BBOS-1A sorbent it is advantageous to time from time introduce a drying step to decrease water content in the sorbent. After drying the BBOS-1A sorbent restores its capacity.

[0097] To decrease sorbent hydrophilicity but still keep its CO2 adsorption capacity at level above mmol CO2/g sorbent we decreased the K2CO3 content increasing PZ loading, BBOS-1B sorbent. Test data are presented in FIG. 3b. The BBOS-1B sorbent was tested only for three adsorption-desorption cycles. The fresh sorbent capacity for BBOS-1B is even slightly higher than for BBOS-1A despite lower K2CO3 content0.7 vs 0.65 mmol CO2/g sorbent, respectively. For the second cycle the sorbent capacity decreases to 0.6 mmol CO2/g sorbent and stays constant for the cycle number 3. This is in line with water content in the sorbent after adsorption step. It increases for cycle 2 and stays at the same level for cycle 3. As we do not see tendency to increase water content further under the experimental conditions applied.

[0098] Second experimental procedure: The sample BBOS-1B was prepared as given above and tested for CO2 uptake capacity by cyclically measuring and integrating the breakthrough curves in a testing unit. To this end an air flow with a controlled CO2 concentration of 450 ppm was passed through a loose bed of 15 g (dry weight) sorbent in a circular reactor of 64 mm diameter and the CO2 concentration was measured using an IR-sensor before and one after the sorbent bed. For desorption the sorbent was subjected to a temperature-vacuum-swing process in a steam atmosphere. Details to the procedure can be found in Table 1 according the following procedure (Table 1).

TABLE-US-00001 TABLE 1 Conditions second experimental procedure Step 4 Step 1 Step 2 Step 3 (optional) Step 5 Purpose of Preparation Heating up Desorption - Vacuum Adsorption Step and evacuation Purge cooling Temperature 40 C. Adjusted to 90 C. Not heated Not heated of reactor wall condensation temp at current steam pressure, max. 93 C. Target temp. As low as Heating up >90 C., target <60 C. Reduced to of sorbent possible to >90 C. 104-110 C. ambient Pressure 80 mbar Target Target Target atmospheric 750 mbar 700 mbar 120 mbar Steam flow 0 1 ml/min 1 ml/min 0 0 Air flow n/a n/a n/a n/a 10 l/min Air conditions n/a n/a n/a n/a % RH (T&RH) 60 (11 cycles); 80 (15 cycles); 45 (9 cycles); T = 20-25 C. Planned 2 min Max 25 min 5 min 5 min + 180 min (initial duration 2 min 9 cycles 120 min) Steam line 120 C., steam 120 C. 120 C. n/a n/a temperature purged Condition for time Reaching time time time moving to pressure in next step reactor or time

[0099] After Step 5 the operation is repeated from Step 1.

[0100] The mechanical stability of the sample was tested by sieving the sample after tests. The weight fraction>500 m; >250 m and <250 m was measured.

[0101] Results of Second Experimental Procedure:

[0102] The testing unit was operating stable making it possible to evaluate the sorbent performance within 35 consecutive cycles at different % RH.

[0103] A summary on cyclic tests is presented in FIG. 4.

[0104] The fresh sorbent capacity tested at RH=60% is high1.15 mmol CO2/g sorbent. It stays stable between 1.01-1.07 mmol CO2/g sorbent during the next 11 cycles except cycle 10, which was measured after a 1 day interruption of the experiment.

[0105] When % RH is increased from 60 to 80, the sorbent capacity decreases but stays within the window 0.7-0.8 mmol CO2/g within 15 cycles.

[0106] There is a slight tendency in the capacity to decrease with the cycles, but as soon as sorbent is brought back to lower RH=45% the capacity is restored and stays constant for the next 10 cycles at RH=45%-0.97-1.02 mmol CO2/g sorbent.

[0107] The average sorbent capacity for different % RH is presented in Table 2.

TABLE-US-00002 TABLE 2 Average sorbent capacity during cycle treatment Number of Sorbent capacity, % RH cycles mmolCO2/g sorbent 60 11 1.05 0.05 80 15 0.77 0.08 45 9 0.97 0.05

[0108] Regeneration of the sorbent by steam heating is reproduciblemax. temperature of the sorbent during desorption is within a rather narrow window 93-96 C. for all cycles tested. It means the sorbent operates within the equilibrium window in terms of water content during adsorption and desorption steps. Desorption is performed by steam and it is a fast process, the main CO2 release is measured within 5 minutes of desorption (FIG. 5). The mechanical strength of the sorbent was verified by sieving tests after the test sequence (35 cycles). The data are presented in the Table 3.

TABLE-US-00003 TABLE 3 Sieving of the sorbent after 35 cycles test (sorbent weight 20 g). Sieve Weight of the % of the size, m fraction, g fraction >500 19.45 97.25 >250 0.45 2.25 <250 0.05 0.5

[0109] The sorbent showed a good mechanical stability with only 0.5% total weight loss as particles below 250 m.

[0110] Conclusions:

[0111] BBOS-1B sorbent showed stable sorption performance and mechanical stability during the tests. The sorbent CO2 capacity depends on % RH in the air stream used for CO2 adsorption. Within the cycle test performed at the same % RH the sorbent capacity is stable. The lowest capacity measured is 0.70 for % RH=80. Desorption by steam heating is very efficient and is finished within 10 minutes. The sorbent is mechanically stable showing weight loss below 0.5% after 35 cycles tested at different % RH.

[0112] Porous Supports Impregnated with Piperazine Only:

[0113] First Series of Experiments:

[0114] Porous supports were prepared using the following schemes:

[0115] Xg(*) of PZ (Piperazine) was diluted in about 3g of demineralized water. To dissolve the PZ at this concentration it needs to be heated slightly (40-50 C.), Y g (*) of support was added to the PZ solution and stirred manually during at least 1 min or as long as it takes for the solution to be adsorbed. The sample was then dried at 105 C. for maximal 30 min in fan oven. PZ adsorbs CO2 well at high moisture levels. The samples are then dried to desired moisture level (for instance 50%, d.b.).

[0116] (*) X+Y=2.5-5 g (dry base)

[0117] In the examples the CO2 adsorption test applied was as follows: Sorbent prepared by the above described method is brought into a tube with a diameter of approximately 20 mm and a height of minimal 100 mm. Air is led through the sorbent at a rate of 15-40 I/g/hr, at a temperature of 15-25 C., and 80% RH (standard condition), 450-550 ppm CO2 until output CO2>80% of input CO2. The breakthrough curve is determined by measuring the CO2 level in the output. The CO2 adsorption capacity (mmol CO2/g Sorbent) is calculated from the difference of CO2 level between the input and output.

[0118] Example A-1: 2.5 g Sorbent (X=1.0 g PZ, Y=1.5 g activated carbon cloth, Hangzhou Nature Technology HNCFC-1200) containing 0.60 g water/g sorbent was brought into the adsorption tube. Air (80% RH, 450 ppm CO2, 20 C.) was led through the tube at a rate of 27 I/g/hr during 135 min. The calculated CO2 adsorption was 0.80 mmol CO2/g sorbent (dry base)

[0119] Example A-2: 5 g sorbent (X=2.0 g PZ, Y=3.0 g activated carbon beads, Kuraray GLC 10*32)) containing 0.33 g water/g sorbent was brought into the adsorption tube. Air (80% RH, 480 ppm CO2, 20 C.) was led through the tube at a rate of 34 I/g/hr during 180 min. The calculated CO2 adsorption was 1.57 mmol CO2/g sorbent (dry base).

[0120] Example A-3: 2.5 g sorbent (X=0.37 g PZ, Y=2.13 g activated carbon cloth, Hangzhou Nature Technology HNCFC-1200)) containing 0.87 g water/g sorbent was brought into the adsorption tube. Air (80% RH, 470 ppm CO2, 20 C.) was led through the tube at a rate of 27

[0121] I/g/hr during 60 min. The calculated CO2 adsorption was 0.22 mmol CO2/g sorbent (dry base).

[0122] Example A-4: 5 g sorbent (X=3.0 g PZ, Y=2.0 g cotton wool)) containing 0.80 g water/g sorbent was brought into the adsorption tube. Air (80% RH, 480 ppm CO2, 20 C.) was led through the tube at a rate of 32 I/g/hr during 280 min. The calculated CO2 adsorption was 1.61 mmol CO2/g sorbent (dry base).

[0123] Example A-5: 5 g sorbent (X=2.0 g PZ, Y=3.0 g alumina, Sasol Puralox TH 100/150) containing 0.75 g water/g sorbent was brought into the adsorption tube. Air (80% RH, 500 ppm CO2, 20 C.) was led through the tube at a rate of 32 I/g/hr during 280 min. The calculated CO2 adsorption was 1.57 mmol CO2/g sorbent (dry base).

[0124] Example B: Same as A but at higher water content.

[0125] Example B-1: 2.5 g sorbent (X=1.0 g PZ, Y=1.5 g activated carbon cloth, Hangzhou Nature Technology HNCFC-1200) containing 1.26 g water/g sorbent was brought into the adsorption tube. Air (80% RH, 470 ppm CO2, 20 C.) was led through the tube at a rate of 27 I/g/hr during 210 min. The calculated CO2 adsorption was 1.27 mmol CO2/g Sorbent (dry base).

[0126] Example B2: 5 g sorbent (X=2.0 g PZ, Y=3.0 g activated carbon beads, Kuraray GLC 10*32) containing 1.21 g water/g sorbent was brought into the adsorption tube. Air (80% RH, 460 ppm CO2, 20 C.) was led through the tube at a rate of 34 I/g/hr during 235 min. The calculated CO2 adsorption was 1.97 mmol CO2/g sorbent (dry base).

[0127] Example B3: 5 g sorbent (X=3.0 g PZ, Y=2.0 g cotton wool)) containing 1.20 g water/g Sorbent was brought into the adsorption tube. Air (80% RH, 480 ppm CO2, 20 C.) was led through the tube at a rate of 32 I/g/hr during 325 min. The calculated CO2 adsorption was 2.03 mmol CO2/g Sorbent (dry base).

[0128] Example C: Samples from series B were tested at 50% and 60% RH showing minimal changes in adsorption capacity. The performance is hardly affected by higher % RH.

[0129] Example D: Activated carbon beads, Kuraray GLC contacted with the liquid phase of pyrolyzed algae result in a sorbent with significant CO2 capturing capability.

[0130] Second Series of Experiments:

[0131] Sorbent Preparation:

[0132] Several sorbent compositions were prepared by impregnation, first on 2.5-5 g scale for direct testing the direct CO2 adsorption at a certain water content. Second, two sorbent compositions were prepared by impregnation on 100 g scale for cyclic CO2 adsorption experiments in the Thermo-reactor and Double Wall reactor. Finally, a 100 g Sorbent composition was prepared by impregnation for testing on the testing unit.

[0133] A general recipe for impregnation procedure is presented in the following. The amounts of ingredients can be adjusted to the desired scale.

[0134] Impregnation method for 40% PZ(Piperazine) on GLC-10*32 AC-beads (BBOS-2):

[0135] Support: Active carbon: GLC-10*32 (Kuraray)

[0136] GLC 10*32 has a PV-H2O (pore volume incipient wetness) of about 2.7 ml/g.

[0137] Procedure for PV-H2O Determination e.g. for Activated Carbon by Incipient Wetness: Activated carbon is dried at 105 C. in a fan oven for 1 hr. 1 g of the dried sample is weighed into a 30 ml flask.

[0138] Water is added in increments of 0.1 ml at room temperature.

[0139] After each water addition the sample is homogenized by shaking.

[0140] When the sorbent sticks to the bottom of the flask when turned around after homogenization, all available pores are filled and incipient wetness is achieved, expressed as: ml water/g sorbent.

[0141] When impregnated with a viscous concentrated solution the available PV can be smaller, or it will take more time for the solution to be absorbed. So, for every impregnation mode one should look what is the optimal amount of solute. In the case of different PV-H2O the amount of water can be adjusted to meet full pore impregnation.

[0142] While granular samples were characterized as described above for activated carbon cloth an adapted procedure was applied: a carbon cloth sample was heated out at 105 C. in a convection oven and the weight was noted. Afterwards the sample was immersed into water at room temperature until no more bubbles appeared (approx. 1 min). The sample was taken out and tapped dry gently with a paper towel from both sides. Again, the weight was measured and the and the water retention was calculated by dividing the weight gain (i.e. water uptake) by the dry weight and converting to ml/g using the density of water (1 g/ml).

[0143] Support characterization by nitrogen adsorption, PV-H2O:

[0144] Nitrogen adsorption measurements were performed at 77 K on a Quantachrome ASiQ. The mass of the sample used was 0.04-0.13 g, the granular samples were degassed at 150 C., cloth sample at 70 C. under vacuum for twelve hours before measurement.

[0145] BET (Brunauer, Emmett and Teller) surface area analysis was done using the method ISO 9277. The experimental characterization of micro- and macropores is described in ISO 15901-2 and ISO 15901-3 using the T-plot method for micropore volume (data points in the range p/p 0=0.2-0.5; thickness calculation according to DeBoer: t()=[13.99/(log(p.sub.0/p)+0.034)]{circumflex over ()}1/2).

TABLE-US-00004 TABLE 4 Porosity N2 ads/des Flexzorb HNCFC- HNCFC- GLC FM-100 800 1200 10 32 pk-1-3-m Micropore- ml/g 0.395 0.377 0.464 0.625 0.365 T-plot volume* Micropore- m2/g 978 972 1181 1466 902 T-plot area* BET-Specific m2/g 1041 1021 1259 2079 1026 Surface area* Pore ml/g 0.45 0.42 0.54 1.59 0.52 volume* PV-H2O(**) ml/g 2.7 1.12 Water ml/g 1.32 1.82 1.76 retention *** *measured by Nitrogen adsorption (**)measured by pore volume impregnation *** measured as described above

[0146] Flexzorb FM-100 is an activated carbon cloth, and is available from Chemviron Carbon, UK. HNCFC-800 and 1200 are activated carbon cloths, and are available from Hanghzou Nature Technology Co., Ltd, China.

[0147] GLC 1032 is an activated carbon granulate (0,5-1.7 mm), and is available from Kuraray Co., Ltd, Japan.

[0148] pk-1-3-m is an activated carbon granulate (1-3 mm), and is available from Cabot Norit Nederland B.V.

[0149] Pore Volume Impregnation in a Glass Beaker:

[0150] 2 g of PZ was diluted in about 6 g of demineralised water. To solve the PZ at this concentration it needs to be heated slightly (40-50 C.). 3 g of AC-beads was added in 1 sec and stirred manually with a spoon during at least 1 min or as long as it took for the solution to be adsorbed.

[0151] Sample was dried at 105 C. for maximal 30 min in fan oven.

[0152] Since PZ adsorbs CO2 well at high moisture level we only dry the sample to the desired moisture level (for instance, 50%, d.b.).

[0153] Small Scale Direct Tests:

[0154] A series of sorbents were prepared on 2.5-5 g scale on different supports and at different levels of PZ and water content.

[0155] In table 1 an overview is presented of the selected supports.

[0156] These supports were selected for their high pore volume necessary to store high amounts of PZ and water and still maintain good accessibility.

[0157] CO2 Adsorption Experiment: For the experiments, 2.5-5 g sorbent is brought into a tube with a diameter of approximately 20 mm and a height of minimal 100 mm.

[0158] Air is led through the sorbent at a rate of 15-40 I/g/hr, at a temperature of 15-25 C., and 80% RH (standard condition), 450-550 ppm CO2 until output CO2>80% of input CO2.

[0159] The breakthrough curve is determined by alternatively measuring the CO2 level in the output and input.

[0160] CO2 adsorption capacity (mmol CO2/g Sorbent) is calculated from the difference of CO2 level between the input and output, sample weight and air-flow.

[0161] In FIG. 6 the CO2 capacity is plotted of several samples against the water content (wt % dry base). The experiments show the following:

[0162] GLC-1032 beads show the highest CO2 capacity. Maximum capacity (3.0 mmol/g) is reached at a 60 wt % PZ level.

[0163] All Carbon cloths show lower CO2 capacity than GLC beads. It is expected that the carbon cloths, due to their very high porosity, reach their maximum CO2 capture capacity at PZ>60 wt %.

[0164] Generally, we observe a tendency to higher CO2 capacity at higher water content of Sorbent.

[0165] In one case (carbon cloth HNCFC-1200, brown line) we tried a steam desorption on small scale, which showed a slightly lower capacity after regeneration at higher water content. We observed a high pressure drop over the wet sorbent bed that might have had a negative effect on the measurement of the regenerated sorbent.

[0166] As a cheap alternative we tried cotton wool as support for impregnation (60 wt % PZ) with PZ solution. The observed CO2 capacity was lower than the carbon cloth but still very high (2.0 mmol/g) for such a simple and cheap system. This observation means that, under wet conditions, we do not necessarily need a specific porous system for CO2 adsorption but any support that can hold the PZ solution on its surface can do the job. Relevant here is a good wetting of the support similar to what is known from trickle bed reactor operations (for criteria to be observed reference is made to: Review on criteria to ensure ideal behaviors in trickle-bed reactors, Mederosa et al. in Applied Catalysis A: General 355 (2009) 1-19).

[0167] Cyclic Tests:

[0168] For running cyclic tests on the Thermo-reactor we prepared 100 g of Sorbent with 40% PZ on GLC-1032 beads according to the procedure described above.

[0169] Cyclic measurement of CO2 capacity in Thermo-reactor.

[0170] CO2 capture from ambient air has been performed in a thermo-reactor (dewar vessel) to prevent heat exchange between the sorbent and environment during the desorption step (FIG. 2). About 100 g of the sorbent was placed into the reactor. CO2 adsorption tests were performed with ambient air (led through a moisturizer to adjust the airflow to 75-85% RH). Adsorption time 5h was applied due to limitations in the air-pump capacity. The exact experimental conditions are shown in the corresponding pictures with the experimental data. CO2 sorbent capacity was measured following CO2 concentration at the reactor outlet during the adsorption experiment.

[0171] Desorption was performed with steam generated in a round bottom flask and directly introduced into the space above the sorbent bed. There is a widening in the inlet tube to prevent droplets of condensed steam to be carried with the steam flow. When steaming starts a condensation-front moves upwards until the whole inlet tube is at 100 C. Then the steam is introduced into the sorbent space, heating up the sorbent bed by releasing the condensation heat.

[0172] When the whole bed is heated to >100 C., steam exits through the outlet effectively stripping of the released CO2. Due to the used design we did not observe any liquid water. Desorption temperature was between 100-115 C., at 1 bar. Desorption time was 1 h. CO2 released during the desorption was not measured.

[0173] Water content in the sorbent was estimated at the end of adsorption and desorption cycle gravimetrically from the reactor weight.

[0174] Results of cyclic tests in Thermo-reactor:

[0175] To determine the sorbent performance during the cyclic tests ambient air flow with 80% RH was used. Data for CO2 capacity and water content in the sorbents tested are presented in FIG. 7.

[0176] We observe no build-up in water level during 3 des/ads-cycles. The water levels stabilize at during each cycle (black dotted line). The blue line shows the water build-up of BBOS-1 sorbent(36% K2CO3/9% PZ).

[0177] The CO2 capacity shows some variation (squares with red lining) but is on average>1 mmol/g.

[0178] Cyclic Measurement of CO2 Capacity in Double-Wall Reactor:

[0179] For running cyclic tests on a Sorbent prepared with Cotton wool as support, 194,5 g of a 15 wt % solution of PZ was impregnated by spraying it over 38 g of layers of cotton wool(40 wt % PZ).

[0180] These impregnated cotton layers were dried at 105 C. for 30 min.

[0181] Cyclic measurements were carried out in the same mode as described above, with the exception that another sorbent reactor was used, as described below.

[0182] The layers of impregnated cotton wool were carefully placed in the double wall of the reactor forming a vertical sorbent bed around an interior cylinder. In the Ads mode; air (80% RH) is introduced in the interior space, passes through the sorbent bed to the exterior space and leaves through the outlet. In the Des mode; air outlet is blocked, an amount of water is weighed into the bottom of the pan (exterior space), and pan is heated on a hot plate resulting in a steam flow forced through the sorbent bed to the interior space, leaving through the central outlet (air inlet). Exterior of reactor is thermally insulated to prevent excessive condensation on the outer wall.

[0183] This mode of testing for the impregnated cotton wool layers was chosen because it will ensure proper gas/sorbent contact to achieve maximum capacity.

[0184] Results of Cyclic Tests in Double-Wall Reactor:

[0185] To determine the sorbent performance during the cyclic tests ambient air flow with 80% RH was used. Data for CO2 capacity and water content in the sorbents tested are presented in FIG. 8.

[0186] Starting from a relative low water content, we observe a strong increase during the first 3 cycles to end up at a stable level of 90-110 wt % water during the following cycles.

[0187] Although the water level is 30% higher, capacity is on the same level as the GLC sample, 0.9-1.1 mmolCO2/g.

[0188] After 6 cycles we observe a slow decline in capacity from >1 to <0.8 mmol CO2/g. After opening the reactor, we found that the lower part of the vertical sorbent bed contained more than the double amount of PZ than the upper part. Since the water/PZ solution is not contained in a porous system but contained in between fibers, the pull of gravity will provoke a slow movement of the liquid phase from top to bottom, making CO2adsorption less effective because the top part, that contains less PZ, will be saturated with CO2 much faster than the bottom part of the vertical sorbent bed.

[0189] Data from Testing Unit:

[0190] A sample 40% PZ on GLC-1032 was prepared according to the procedure given above and tested in a protocol similar to the one outlined in Table 1.

[0191] Run 1 is a successful run with desorption capacity 1.58 mmol CO2/g sorbent and adsorption capacity 1.8 mmol/g dry sorbent.

[0192] Further runs were successful tests which show high stable sorbent capacity between 1.48-1.52 mmol CO2/g sorbent.

SUMMARY

[0193] These tests illustrate well the sorbent performance under the adsorption conditions tested: 80% RH. Despite some deviation in the experimental procedure, the sorbent shows stable performance during the runs with a high CO2 capacity 1.48-1.52 mmol CO2/g sorbent. From the data we can concludeafter 12 cycles adsorption desorption cycles the PZ-AC sorbent showed stable performance at the level 1.5 mmol CO2/g in average.

TABLE-US-00005 LIST OF REFERENCE SIGNS 1 ambient air, ambient air inflow structure 2 outflow of ambient air behind adsorption unit in adsorption flow-through mode 3 sorbent material 4 steam, steam inflow structure for desorption 5 reactor outlet for extraction 6 vacuum unit/separator 7 wall 8 reactor unit