Innovative Catalytic Technologies & Materials for Next Gas to Liquid Processes

Final Report Summary - NEXT-GTL (Innovative Catalytic Technologies & Materials for Next Gas to Liquid Processes)

Executive Summary:

NEXT-GTL addresses main cost drivers and technical barriers of the conventional GTL process. The main objectives are:

• To reduce the cost and energy consumption of syngas production, and overcome the stability related barriers in using catalysts in this process
• To develop GTL technologies suitable for small-medium scale productions in remote NG areas
• To develop processes for producing liquid fuels which can be blended in both gasoline and diesel pools, or which may be used for chemical purposes.

Accordingly, three development lines are followed in this project:

Line 1: advanced, low temperature route for catalytic syngas formation from natural gas, in which where reaction steps are integrated with different types of membranes for O2, H2 and CO2 separation.

Line 2: direct low temperature catalytic conversion of methane to methanol/DME, utilizing several innovative concepts to overcome the drawbacks of previous approaches including the use of supported ionic liquids/molten salts

Line 3: direct catalytic conversion of methane to aromatics under non-oxidative conditions followed by upgrading of the products by alkylation with ethane/propane.

Project Context and Objectives:

NEXT-GTL general objective is to address the main cost drivers and technical barriers of the conventional gas-to-liquid (GTL) process. Three were the main specific objectives:

- To reduce the cost and energy consumption of syngas production, and overcome the stability related barriers in using catalysts in this process
- To develop GTL technologies suitable for small-medium scale productions in remote NG areas
- To develop processes for producing liquid fuels which can be blended in both gasoline and diesel pools, or which may be used for chemical purposes.

Accordingly, three development lines are followed in this project:

Line 1: advanced, low temperature route for catalytic syngas formation from natural gas, in which reaction steps are integrated with different types of membranes for O2, H2 and CO2 separation.
Line 2: direct low temperature catalytic conversion of methane to methanol/DME, utilizing several innovative concepts to overcome the drawbacks of previous approaches
Line 3: direct catalytic conversion of methane to aromatics under non-oxidative conditions followed by upgrading of the products by alkylation with ethane/propane.

Line 1 aims at the improvement of the current gas to liquid (GTL) conversion chain by developing an improved technology for the most costly and energy-intensive step of syngas production.

Lines 2 and 3 address alternative direct routes (i.e. not via syngas) of methane to liquid conversion to transportable fuels, suitable for both gasoline and diesel pools, and potentially for chemical uses; both oxidative and non-oxidative routes for methane conversion are explored to compare the two alternatives.

The specific final objectives of these three lines of activities were thus different:

- Line 1: develop an optimized new process schemes, based on the integration with membranes, and demonstrate the validity of the approach in a new build small-size pilot unit
- Line 2: develop innovative catalysts for direct methane to methanol conversion, and analyse the techno-economic suitability of development of a process based on actual results
- Line 3: develop novel catalysts/membrane for direct catalytic conversion of methane to aromatics under non-oxidative conditions and for upgrading the products by alkylation with ethane/propane, and analyse the techno-economic suitability of development of a process based on actual results

All these specific final objectives were met in this project. In addition to these three core activity lines (each corresponding to a specific WP), a fourth WP (WP4) was dedicated to made a comparative techno-economic assessment of the results of the three lines of activities, as well as to verify possible synergies. Also these objectives was achieved in this final reporting periods.

Two additional WPs complete the project, one dedicated to dissemination and the other to scientific and project management. For dissemination (WP5), in addition to many publications, presentations at conferences and patents, various activities were organized, between which to mention the organization of a workshop (on use of CO2), the organization of an international school (on the use of membrane for novel process engineering) and a book (in preparation) summarizing the key (non-confidential) results of the project.

All deliverables and milestones in the DoW (according to last amendment) were achieved. All partners, except one retired from the consortium, actively participated in preparing deliverables and achieving milestones.

The consortium partners comprise leading companies and research groups, with core competences in catalysis, membranes and reaction engineering, to ensure strong interdisciplinary work at the different stages of theory/modelling, material development and characterization, testing, material/reactor engineering, and process development.

Project Results:

During this final period of the four year NEXT-GTL project, the following main progresses have been achieved:

Line 1

The new process architecture to produce synthesis gas from methane partial oxidation integrated with different types of membranes for O2, H2 and CO2 separation was finalized. This novel process scheme allows to operate at lower temperature with respect to conventional scheme, thus reducing the oxygen demand for partial oxidation stage and at the same time improving the life-time of the catalysts and minimizing overall energy consumption for syngas production.

Together with the development of a proper process scheme with heat and material balances for large capacity applications, the experimental activities performed for the preparation and optimization of the catalysts and gases separation membranes and the efforts for the relative scale-ups, a pilot scale experimentation was also performed to assess the feasibility of the concept.

In order to lower the operating temperatures, the concept of multi-staging CPO reactors was applied, with each reaction step followed by a H2 metallic membrane. Such configuration enables for a substantial reduction in natural gas consumption (< 8%) implying an equivalent reduction of CO2 emissions.

In addition to H2 membranes integrated in the pilot unit, small-scale pilot units for O2-separation membranes and for CO2 separation/recovery were also developed.

Line 2

The activities continued along the lines previously defined devoting more efforts to basic activity for the development of suitable methane activation sites. In addition, an economic evaluation of a process to produce methanol by direct oxidation of methane has been performed.

The activities on the catalyst development were focused at i) development of the C-H activation component, ii) development of the oxidation-active centres, iii) theory and modelling for an optimal design of the catalyst, iv) development of Cu-zeolite catalysts and catalysts testing and ranking, as well as analysis of the catalyst stability and optimal performances-

A techno-economic evaluation on a possible industrial process for the direct CH4 to MeOH/DME conversion based on the experimental data produced within the project has been finalised.

Line 3

The activities were centred on the evaluation of the catalyst stability and long-term performance, including the use of different oxidants during regeneration cycles and the identification of an optimal regeneration sequence. The results allowed to improve catalyst long-term performance. Selected catalysts were scale-up in kg-scale and shown to be both mechanical stable in fluidized bed operation and still selective towards benzene formation. Major achievements were also made on the field of membrane development.

The experimental work was accompanied by process layout engineering and economic calculations for different process scenarios as well as different sites (Europe & US Gulf coast). Process schemes and detailed descriptions for the reactor, liquid/gas and gas/gas separation were identified as well as the scenarios for economic uses of the technology. Key performance indicators for a technical feasible and economic attractive process were also identified.

WP4 - Comparison of the technology lines

In this final period, in addition to previous activities to foster cross-collaboration and exchange of information between the above three lines, this WP made a comparative evaluation and assessment of the above three technology lines. A report on the “Critical comparison of the three process options to convert NG to liquid transportable fuels” was prepared. This deliverable provided a summarized technical and economic assessment of the three technical lines investigated in the NEXT-GTL project.

WP5 - Dissemination

Activities in this WP were related to foster dissemination of the project results, both in the conventional way (lectures and posters at relevant conferences, publications in scientific journals and the public website), and by organizing specific events. Between these

- In cooperation with other European projects the International Workshop NAno Porous Materials for ENergy and ENvironmental Applications (NAPEN 2011) held in Rhodes, Greece, on 9-12 June 2011,
- A colloquium on Chemical Reaction Engineering for methane valorization, organized jointly by OCMOL and NEXT-GTL in Munich, Germany on October 10 and 11, 2011
- Workshop “CO2: Valuable source of carbon”, (April 16 2012), organized by Tecnimont-KT and NEXT-GTL in Rome.
- Summer course „Decoding the Complexity of Chemical Reactions at Ghent University, Belgium from June 25 to June 29, 2012.
- Summer School "Engineering of membrane reactors for the process industry", held on October 3-6, 2013, in Sarteano (Siena, Tuscany), organized by partner KT in the frame of NEXT-GTL activities

Other activities were related to impact on Horizon 2020 and related preparation roadmaps, and other activities inside ERA, and clustering activities with CMOL and other EU projects. With OCMOL a book (published by CRC Press) is in preparation with the tentative title “Recent advances in Gas to transportable liquids “. The book aims to provide scientists gain insight on the recent advances in gas to liquid and carbon dioxide capture processes and can be used as tutorial for relevant workshops.

Potential Impact:

NEXT-GTL aims to contribute to develop key knowledge for novel innovative catalytic routes to convert methane to liquid fuels. The three different routes have different level of advancement towards exploitation, in relation to the different challenges.

In line 1, the final results will be pilot plant results on the new process scheme, which allow a techno-economic evaluation of the new process scheme. The specific outputs will be the basic process layout and assessment of the novel low temperature process for syngas production.

In line 2 the expected final result will be the availability of an improved catalysts for direct methane to methanol with the data on performances, productivity, selectivity and short-term stability necessary for an estimation of the techno-economic feasibility of the new process, taking into account the increased interest on transforming directly methane to methanol due to shale gas availability which has break down cost parity between oil and natural gas, decreasing significantly the cost of the latter.

In line 3 the expected final result will be the availability of an improved catalyst for methane aromatization, with reaction conditions to minimize deactivation, and data on catalyst productivity, selectivity and stability necessary for an estimation of the techno-economic feasibility of the new process. Indication of the advantages and problems of integrating membranes in the process scheme, also with some new idea which is explored in the project, will be available. Data on the novel process of benzene alkylation using C2-C3 alkanes will be also available. A patent was issued which is actually exploited within the consortium.

In addition to process data and advanced catalysts, new membranes for H2, O2 and CO2 separation will be available.

The project strategic impact will be thus on the following main aspects:

1. Contribute to the diversification of raw materials in refinery AND petrochemistry.
2. Use natural gas to reduce the dependence on raw oil.
3. Produce higher quality fuels: (a) sulphur free, (b) high octane or cetane components for gasoline AND diesel pools.
4. Improve the efficiency of use of natural gas by: (a) enabling valorization of NG which is flared or not used, (b) developing novel processes/technologies to use small-medium gas fields which cannot be economically exploited with current technologies.
5. Improve the efficiency of natural gas subsequent processing by: (a) developing a novel process for low temperature syngas which is expected to increase the energetic efficiency of the process of 10%, (b) developing direct (low temperature) oxidative routes of methane conversion which are expected to increase carbon efficiency of the process from the current 80-83% to 85-90% allowing thus a significant gain in the energy efficiency and reduction of the emissions, besides to process simplification and reduction of the risks, (c) developing direct (low-temperature) non-oxidative routes for NG conversion which have an intrinsic better energy efficiency for the coproduction of fuel AND H2 with respect the route via syngas and steam reforming.
6. Benefit our environment, safety and health, and stability of energy resources for society and economy by (a) reduction of CO2 emissions and energy consumption in transport and use of natural gas, (b) reduction of NG flares and associated impact on the environment, (c) use of NG resources actually not used to improve the stability of energy resources, (d) provide an alternative to pipelines and LNG for a better geo-strategic stability of energy resources, (e) creating new opportunities for using NG also in chemical production, (f) developing relevant market opportunities for monetization of not-used NG resources, (g) developing membrane and advanced separation technologies for H2, O2 and CO2 which could be used in a variety of other refinery, petrochemistry, combustion and other non-chemical processes to increase their efficiency, (h) incentivising the introduction of new processes and technologies with increased competitiveness of companies with a positive impact on labour market.

List of Websites:

http://www.nextgtl.eu

Final Report Summary - NEXT-GTL (Innovative Catalytic Technologies & Materials for Next Gas to Liquid Processes)

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