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Continuous Production of Amine Derivatives of Green Silica for Carbon Capture

Abdul Wadood Sharif


Supervisors: Dr. Ashleigh Fletcher Dr. Siddharth Patwardhan

Sponsored by: The Carnegie Trust Interns@Strathclyde

The place of useful learning The University of Strathclyde is a charitable body, registered in Scotland, number SC015263

Table of Contents
Acknowledgments Abstract 1 Background on Carbon Dioxide 2 Current Technologies 3 Aims and Objectives 4 Theory 5 Analytical Methods for Characterisation 6 Experimental 7 Results & Discussion 8 Conclusion & Recommendations 9 References 10 Reflective Report 2 3 4 4 5 5 6 6 8 11 12 13

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Acknowledgments
I would like to thank my supervisors, Dr. Ashleigh Fletcher and Dr. Siddharth Patwardhan for their help, advice and encouragement for the duration of the placement. I would also like to personally thank Dr. Thomas Yip for his assistance, input and demonstrations in the laboratory. I would like to express thanks to the University of Strathclyde and the members of chemical and process engineering department for this invaluable opportunity.

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Abstract
With carbon dioxide emissions and mitigation becoming a pressing legal issue for industry, new solutions to the otherwise costly, established method currently used must be investigated. Alternative solutions include zeolites, activated carbons and amine grafted silica. Although promising these suffer from distinct disadvantages: loss of CO 2 capacity with presence of moisture, low CO 2 /N 2 selectivity and long, toxic, costly production respectively. A new method for production of amine-functionalised silica has been investigated by the Patwardhan group at Strathclyde University. This technique is inspired by biological processes and is a green method: quick reaction completion employs ambient conditions (both temperature and pH) and uses environmentally-friendly reagents. The aims of this report were to optimise the batch process of production and then investigate different methods of continuous production of the amine-silica sorbent using a plug flow reactor with poly(allylamine hydrochloride) as the amine adsorbent. Following reaction, the products were centrifuged and washed with deionised water three times and then allowed to dry in an oven overnight. From the results the yields for both the batch and semi-batch process were found to be the highest. This was due to the accuracy of the pH achieved (7 0.05) and the extended reaction time during the first centrifuge. The yield was a little lower for the batch run with excess acid at the end as the excess acid prevents further aggregation and this indicated that longer times should be given for full aggregation. The lowest yield was found with flow runs mostly due to the lack of pH measurement due to the excess acid present. Intelligent gravimetric analysis results indicated that the presence of amine in the samples were crucial for CO 2 uptake. All samples exhibited peaks at 1055 1035 cm-1 and 1545 1520 cm-1 from FTIR analysis. The former represents the presence of Si-O-Si bonds while the latter indicates NH bonds. This implies that there is both silica and amine present in samples. Further work includes CHN analysis for nitrogen loading, BET for porosity and surface area analysis and further IGA for CO 2 uptake of flow samples.

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1 Background on Carbon Dioxide


Global climate change due to greenhouse gas emissions is one of the key issues faced by industry today. Although many greenhouse gases exist, such as methane, the most significant is carbon dioxide, due to its abundance. The most recent estimate for carbon dioxide emission is approximately 530 million metric tons (2010) for the United Kingdom. [1] With the introduction of legislation (Climate Change Act 2008), the United Kingdoms target for 2050 is to reduce carbon emissions by 80% from the 1990 baseline (approximately 600 million metric tons).[2]

2 Current Technologies
2.1 Amine scrubbing
Currently the most established and widely-used method of carbon capture is the process of amine scrubbing. During this process flue gas, which is generated from combustion of fossil fuels and contains mainly carbon dioxide, nitrogen and water, is passed up through an absorption column whilst a liquid amine is pumped to the top of the column and passed down. The amine absorbs the carbon dioxide and must then be regenerated for further use.

Figure 1 Amine Scrubbing Diagram

Although widely implemented, the process suffers from one main disadvantage. This process is expensive, costing approximately $50 per ton CO 2 removed or 30% of the power generated by a power plant.[3] This cost is associated with high energy required for regeneration of the amine at the reboiler stage and the power for pumping.

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2.2 Emerging Solutions


Table 1 Comparison of possible solutions for carbon capture

Solution Zeolites[4]

Advantages High Capacity (3-4 mmol/g)

Disadvantages Performance suffers with moisture. Low CO 2 /N 2 Selectivity (bad for flue gas)

Activated High Capacity (8.59 mmol/g) Carbons[5] Amine Grafted Silica[6][7]

High Capacity (Up to 7.9 mmol/g) Unfavourable reaction conditions: o Harsh pH Favourable repeatability cyclic o High temperatures tests. o Toxic materials Low Regeneration temperatures. o Long reaction times Quick uptake (~10 mins) o Multi-step Process

Above lists some emerging solutions to the issue of carbon capture, although more exist such as membranes[REF: Pennline] and metal organic frameworks [REF: mason]. Highlighted is amine-grafted silica, which shows promising capabilities but suffers from complicated, toxic

3 Aims and Objectives


The main aims of this study were: 1) Study of batch manufacture of bio-inspired silica materials (See section 4.1) 2) Optimisation of batch processes for process scale-up 3) Study of flowing manufacture with different arrangements These objectives were met by a combination of synthetic processes and characterisation of products to ensure the composition and properties were unaltered by the processing conditions. Characterisation methods included product yield, FTIR analysis and IGA analysis (See Analytical Methods for Characterisation).

4 Theory
4.1 Bio-inspired Green Silica
To combat the problems faced by amine-silica production the Patwardhan group have utilised a biologically inspired procedure. Using a biologically inspired component (amine), it is possible to imitate nature. Furthermore the method of production is green: it employs ambient conditions, non-toxic materials and relatively quick reaction time (5 minutes). The procedure involves reacting an amine and silica precursor together at neutral pH (pH=7) which can be achieved via a titration with 1M HCl acid. Aggregation is best promoted at this pH. Further addition of acid to a obtain pH 2 results in a situation akin to freezing of aggregation. This is due to the interactions between the amine and precursor being less favourable in extreme pH. Page 5

For a material to be a viable candidate for carbon capture, it must be readily scaled up with as few complications as possible. Production of amine-grafted silica is difficult to scale up due to extreme conditions, toxic materials, long reaction times and multi-step process. The advantages of the green process should allow for promising scalability for large production.

4.2 PAH - Poly(allylamine hydrochloride)


The amine used for investigation was poly(allylamine hydrochloride) or PAH with average molecular weight of 15000 g/mol.

Figure 2 Molecular Structure of PAH

PAH was used as the amine component since previous investigation performed by the group highlighted PAH as one of the most promising for carbon capture. [8] Additionally, further research into PAH indicated this amine gave the highest yield in solid produced via batch synthesis. [9]

5 Analytical Methods for Characterisation


5.1 Intelligent Gravimetric Analysis (IGA)
By employing IGA it is possible to investigate the CO 2 adsorbed on to the material surface in mmol/g. The intelligent gravimetric analyser is capable of measuring uptake by exposing a known quantity of sample with CO 2 and then precisely measuring the weight difference. For the purposes of this study, the CO 2 was exposed at 100 mbar, the industrially relevant pressure.

5.2 Fourier Transform Infrared Spectroscopy (FTIR) analysis


FTIR analysis was used to determine whether Silica and Poly (allylamine Hydrochloride) was present in the samples generated. By obtaining an infrared spectrum of absorbance, peaks can be assigned to a fingerprint region from literature, this in turn indicates which bonds and hence molecules are present.

6 Experimental
6.1 Reagents used
Sodium metasilicate (Na 2 SiO 3 .5H 2 O) and Sodium Hydroxide (NaOH) pellets (99% purity) were purchased from Fisher Scientific. The amine polymer poly (allylamine hydrochloride) with average molecular weight 15,000 g/mol and 1M hydrochloric acid were purchased from Sigma Aldrich. Deionised water was readily available.

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6.2 Experimental procedure


6.2.1 Batch Synthesis

Sodium metasilicate and PAH was weighed out to obtain a 30 mM solution on a 50 ml (0.3182 g) basis and 1mg/ml (0.05 g) solution respectively. 25ml deionised water was added to the sodium metasilicate and 22.5 ml deionised water was added to the PAH. The solutions were mixed separately then added together and after 1 minute the pH was recorded every 30 seconds until 5 minutes had elapsed. As this time elapsed the remaining 2.5ml was added in the form of 1M HCl acid in aliquots, this volume was determined previously to ensure an end pH of 7 was achieved (See section 7.1). The solution was transferred to a vial for centrifugation at 8000rpm for 15 minutes followed by washing with deionised water. This was repeated twice more and finally the remaining solid was oven dried at 85C overnight. 6.2.2 Semi-Batch Synthesis (FL)

Figure 3 System Diagram with flows of amine (blue), silica (yellow) and product (green)

All masses weighed and volumetric additions for the batch synthesis were multiplied by four so as to obtain a total output of 200 ml. Sodium Hydroxide pellets were weighed out to obtain a 2M solution on a 50ml basis (4g). The vessels were connected to two peristaltic pumps running at 2ml/min each to emulate a plug flow reactor (PFR). The solutions were mixed together in 3mm i.d. silicone tubing which ensured a 5 minute residence time was maintained. The solution was collected in a vessel until 50ml was collected. The output from reactor was immediately transferred to another vessel and the same time was allowed to pass. This process was repeated twice more. After each 50ml solution had been collected the process of centrifugation as done in the batch process was immediately initiated followed by drying in oven at 85C overnight. Following the complete run (after 4x50ml volume collected), 50ml deionised water was added to the NaOH pellets and allowed to dissolve. The tubing was then purged with this NaOH solution, followed by 1 litre of deionised water for cleansing purposes.

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6.2.3

Flow Synthesis (FLA)

Similar to the fed batch synthesis however 1.3ml HCl acid was added to each collection vessel prior to solution collection.

7 Results & Discussion


7.1 Evaluation of Volumetric HCl Requirement
Table 2 HCl added and pH for batch runs (50ml basis)

Sample Reference PAH-7 PAH-10 PAH-14 PAH-15 PAH-17 Average:

HCl Acid Added (ml) 2.49 2.50 2.50 2.50 2.50 2.50

pH 6.99 6.96 7.02 7.05 6.97

Note: The PAH-7 run was considered an outlier once flow synthesis was attempted. From the above table it can be observed that the HCl added showed excellent repeatability. Although the pH varied slightly, the range was considered acceptable (pH 7 0.05). The small variation resulted in errors associated with initial weighing.

7.2 Yields
Table 3 Number of samples, average mass and yield for PAH-Silica

Synthesis Method Batch Batch w/ Excess Acid Semi-batch Flow

No. of Samples Generated 4 4 16 16

Average Mass (mg) 76 6 56 3 69 2 21 1

Yield (%) 63 5 46 1 57 2 17 1

Considering the higher yields, the highest on average was observed for batch runs, this is expected as these runs had greatest adaptability of acid added and assurance that a pH as close to 7 as possible was realised. Furthermore the aggregation of solid occurred continued during the first centrifugation. The semi-batch process also resulted in a high yield due to the monitoring of pH during reaction and repeated runs allowed for pH near 7 to be attained. Furthermore the extended run time resulted in greater residence time. Page 8

The batch excess acid resulted in a lower average yield than that of both methods that did not involve excess acid additions described above. This was most likely due to incomplete aggregation of solid. The flow run resulted in a considerably low yield. Similar to the batch excess acid run, aggregation was most likely incomplete at the time the solution came in contact with the excess acid. There was also no assurance of good mixing in the plug flow reactor at such low speeds.

7.3 IGA Results

Figure 4 CO2 Capacity for batch, semi-batch, calcined batch and bare silica

Both batch and semi-batch samples resulted in a considerably high uptake. A calcined batch sample (had amine was removed via heating in the presence of air) and MCM-41, or bare silica, were both run with IGA. From the results it can be observed that the amine has a very crucial role to play in the adsorption of CO 2 .

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7.4 Results: FT-IR analysis


1055-1035 a)
1545-1520

b)

c)

Figure 5 FTIR Spectrum for (a) PAH-Silica, (b) PAH and (c) Sodium metasilicate precursor

From Figure 3a) peaks at 1055-1035 indicate Si-O-Si bonds and hence silica. The peak between 1545 1520 represents N-H bonds and this indicates that amine is present in generated samples. Figure 3b & Figure 3c the aligned peaks are further proof of silica and amine presence. Page 10

8 Conclusion & Recommendations


The batch system required a consistent volume of acid for titration (2.5ml) with slight variations in end pH, most likely due to errors in initial weighing. High average yields were observed for semi-batch (57%) and low average yield were obtained with the flow system (17%). The former was possible because of pH monitoring and extended residence times and the latter suffered without these advantages. IGA results indicated that the amine played a crucial role in adsorption of CO 2 . FTIR confirmed the presence of silica and amines in all samples generated. Improvements to be made are higher flow rates and inclusion of a static mixer to ensure good mixing within PFR for flow system. Further work that can be carried out is CHN-analysis for amine loading, BET for porosity and surface area and further IGA studies.

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9 References
[1] S. Choudrie, N. Passant, J. MacCarthy, UK Greenhouse Gas Inventory: National Statistics User Guide (Ed.: D. O. E. a. C. Change), Oxfordshire, 2012. [2] Climate Change Act (2008), (Ed.: U. Government), The Stationary Office Limited, 2008. [3] M. Ramezan, Carbon Dioxide Capture from Existing Coal-fired Power Plants, NETL, 2006. [4] L. Wang, Z. Liu, P. Li, J. G. Yu, A. E. Rodrigues, Chemical Engineering Journal 2012, 197, 151161. [5] M. Radosz, X. D. Hu, K. Krutkramelis, Y. Q. Shen, Industrial & Engineering Chemistry Research 2008, 47(10), 3783-3794. [6] G. G. Qi, Y. B. Wang, L. Estevez, X. N. Duan, N. Anako, A. H. A. Park, W. Li, C. W. Jones, E. P. Giannelis, Energy & Environmental Science 2011, 4(2), 444-452. [7] W. J. Choi, J. B. Seo, S. Y. Jang, J. H. Jung, K. J. Oh, Journal of Environmental SciencesChina 2009, 21(7), 907-913. [8] D. Prentice, A study of amine activated silica adsorption capabilities & the parameters of evaporation, University of Strathclyde, Glasgow, 2011. [9] C. Scott, Developing Novel Adsorbents for Carbon Capture Technologies, University of Strathclyde, Glasgow, 2012.

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10 Reflective Report
10.1 Presentations
Every fortnight the group was required to present at progress meeting to their supervisor (since I had two supervisors this resulted in a progress meeting each week). During these meetings we were required not only present our progress but also critically analyse others work and our own. It was also an opportunity to raise questions to others and offer help in some areas. This was particularly useful for my project as there were several people working on similar projects and others findings were often useful for my own work and vice-versa. During my placement I was able to improve on presentation skills and also ask relevant questions pertaining to the subject matter.

10.2 Conferences
Throughout my placement, my supervisors would invite myself and others from their group to conferences. Through these conferences we were able to observe current research developments and efforts by companies in particular fields. By attending these conferences, the group was given the chance to see others work and showcase our own. Furthermore these conferences gave the opportunity for myself to network and discuss my project to others. This improved communication skills as when an individual was unfamiliar with the background and area of my research I had to show versatility in my explanation for them to understand what I was doing.

10.3 Self-teaching
Initially, I was very unfamiliar with many aspects of my project: alternative solutions, theory behind analytical methods, previous work etc. Although some guidance was given with regards to these, often I had to find published papers for myself via Web of Knowledge for educating myself with regards to these topics. For previous work done by the group I was given these papers to read through and learn what were the limitations and techniques often used to characterise the samples. This method of learning was very satisfying and having relevant papers I was able to prepare for the technical report at an early stage.

10.4 Innovative thinking


Many problems were faced for the duration of my placement, some of which have still not been overcome at the time of writing. One particular example is of the systematic failure of an expensive piece of equipment, known as FlowSyn. This was the continuous flow reactor which was anticipated to be used for all flow synthesis of material. By meeting with my supervisor and discussing the issue we came to the conclusion that we could use a set of pumps and tubing to obtain a make-shift reactor that could be used instead. These situations I consider one of the most crucial invaluable practical experiences I obtained. It allowed me to develop my problem solving skills unlike any coursework had done thus far.

10.5 Overall Experience


I found the placement to be highly enjoyable both from an educational and practical experience. My assumptions on what research life would pertain to were quickly proven wrong. I found the social aspect to be pleasant and helpful with group lunches and departmental barbeques organised. Although I hope to experience an industrial placement first, I would be interested in continuing research by pursuing a PhD.

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