IMPROOF .

This report presents a description of two renewable fuels, biogas and bio-oil. In a first part, their ways of production and their composition are described. In a second part, a bibliographical review of the experimental studies published on the gas-phase oxidation and combustion of the reactants proposed as surrogates for the components of these renewable fuels are presented.

 The goal of the task is to characterize the composition of the fuels, especially the renewable ones. The first step is the identification of the proper renewable fuels, accounting for the specific needs of the different burners. Once identified the fuels, the characterization results of particular importance in the case of (hydrotreated) bio-oils, whose composition is not completely known. This characterization will allow the identification of a proper surrogate of a limited number of reference species, whose combustion kinetics will be experimentally and theoretically investigated.

The IMPROOF project is a European project aiming at improving the energy efficiency of steam cracking furnaces by developing new techniques to reduce coke and using high emissivity coatings to reduce emissions of greenhouse gases and pollutant emissions. In addition, biogas and bio-oil will be investigated to be used as alternative fuels because they are considered renewable, and hence, can decrease net carbon dioxide production. Today, because of the current economics, the industrial partners do not fully see the potential of using renewable fuels such as bio-oils or biogas for steam cracking. The project will definitely create insight on this matter. For biogas, there is a clear potential but here the cost is still the critical issue. At present, the cost for biogas is still 3 times higher than the conventional gas with the same quality.

To achieve the objectives, LRGP-CNRS laboratory has carried out extensive experimentation collecting reliable experimental data on biogas, bio-oil and natural gas. In parallel, POLIMI has performed a literature study, updating their reaction mechanism for different types of combustion. The objective was focused on three major topics: the study of renewable fuels, as potential candidates to feed the nextgeneration steam-cracking furnaces; the analysis of NOx formation from such fuels; the exploration of unconventional, oxy-combustion burning conditions, such to minimize NOx emissions.

This report presents the analytical techniques and the data set of experimental measurements under all the different operating conditions and for all the studied fuel mixtures.

O. Herbinet et al. (CNRS & POLIMI)

The origin and composition of Biofuels have been precisely defined and explained in Deliverable 1.1. Using such biofuels in process burners for typical petrochemical applications can be challenging as generally large amounts of inert components (CO2, N2, H2O) are present in those fuels. Those large amounts of inerts can cause burner instabilities, as these inerts are lowering the combustion flame temperature. Referring the table 1 on page 7 of the deliverable D1.1 (see Annex), the Biogas mainly consists out of Methane and CO2. The CO2 composition can vary from 19 to 38 vol% depending if it is gained from household or agricultural waste for example.
The project under deliverable D2.1 shall demonstrate the combustion of those fuels and their influence on process parameters like emission, burner stability and heat flux inside the firebox. In addition to the combustion of the Biogas, oxyfiring operation shall be evaluated. Under oxyfiring it is understood that the fuel gas is burned using pure or diluted oxygen, rather than oxygen contained in the surrounding air. The benefit of using pure O2 is that nitrogen, which is making 79 vol% of surrounding air, is depleted, and is therefore not available during the combustion process. This should result in quasi non-existing NOx emissions of the complete fired system.  

The main goal of Deliverable 2.2 is to provide DOW with the necessary information to select which technologies to implement on TRL6. Various technologies including an aluminum containing high temperature alloy, different 3D reactor technologies and high emissivity coatings were tested on a laboratory and/or pilot plant scale. The experimental results in combination with the performed simulations provided a sound basis on which DOW selected the most proven technologies for TRL6 implementation. However, Deliverable 2.2 extends beyond the DOW demonstration furnace and aims to put forward the most promising technologies for future research. Deliverable 2.2 will not go in too much detail on high emissivity coatings since this is discussed extensively in Deliverable 2.5.  

The objective of this report is to document the production of reactor materials (laboratory test coupons) and the coils for the pilot plant at UGENT (TRL5) by S+C. Beside bare tubes also 3D-Technology SCope® is to be tested.

For a qualitative assessment of the coking resistance of industrial reactor materials S+C is requested to provide four different industrial reactor materials for a smaller scale setup (laboratory test coupons) to UGENT. Two out of the four materials will be selected for the production of coils for the pilot plant (TRL5).

Not explicitly mentioned as deliverable but strongly linked to the above mentioned activities (and thus already considered work in the planning) is the provision of additional test coupons for emissivity measurements and coating. Trials on coating are needed to verify if any harmful interaction between coating and tube material will take place or if the coating intends to spall-off during service.

It is the objective of this report to document the production of high emissivity coatings on the pilot plant radiant walls and smaller pieces of refractory.  The dimensions of the pilot plant and the small distance between coated high emissivity radiant walls required assessment. What was the impact of high emissivity surface radiating on themselves at short distances with minimal load present in the furnace?
In the Task 2.3, the benefit of high emissivity coatings on improving refractory materials thermal effectiveness will be demonstrated. Further benefits are expected by coating the pilot reactor radiant walls.
CRESS applied the high emissivity coatings on the pilot plant walls and smaller pieces of refractory for high temperature soak to determine their thermal stability and effective emissivity assessment. An assessment of different product types was accomplished utilizing Emisshield IP-556, ST-25, DI-1, DI-5 and DI-7.  

Different high emissivity coatings developed by Emisshield have been tested for their applicability in the DOW demonstration furnace (TRL6) and the UGent pilot plant (TRL5). Ghent University, Schmidt & Clemens, CRESS/Emisshield and DOW have performed various experiments on different scales to assess which Emisshield high emissivity coating is best suited for the IMPROOF project. The DOW CUP furnace has previously been selected as the demonstration furnace for the IMPROOF project (Deliverable 4.1). Deliverable 2.5 aims to put forward one coating suitable on the demonstration furnace refractory and another high emissivity coating that is applicable on the Centralloy® HT E reactor coils (Deliverable 2.2). The different experiments performed at different research facilities include total hemispherical emissivity measurements, spectral normal emissivity measurements and exposure experiments to air, artificial combustion air and pilot plant conditions.  

The main goal of Deliverable 2.6 is to disseminate the results obtained within this work package related to light olefin yields and coking behavior of 3D reactor technologies. This Deliverable 2.6 combines both experimental results performed on a pilot plant scale and computational fluid dynamics simulations of the same geometry. Successful results at TRL5 will incentivize the industry to implement these 3D reactor technologies at an industrial scale. Deliverable 2.6 can be viewed as an extension to Deliverable 2.2 where coking experiments were performed on a laboratory scale to select the most promising high temperature alloy. To accurately assess coke formation on reactors with a specific 3D design, these laboratory coking tests, where coke deposition on a small coupon is measured over time in a controlled environment, are no longer the best option. To accurately capture the process dynamics, pilot plant experiments combined with computational fluid dynamics simulations have been performed to study coke deposition and product yields. 

In the current study, Large Eddy Simulation (LES) of the reacting flow inside steam-cracking coils have been performed. The objective was first to describe and understand the deep interactions between turbulence, chemistry and heat transfer in various internal geometries (smooth BARE tube, SFT and SCOPE). In particular the impact of the shape of the tube wall on heat transfer and pressure drop is of particular interest. Indeed, the process efficiency is highly sensitive to these phenomena: high heat transfer is desirable to favor the heating by the furnace flame, while keeping the pressure drop as small as possible facilitates the flow motion. As a consequence, a second objective was to apply optimization algorithms to the tube geometry in order to find the shape that leads to the best performance. 

In order to properly assess the impact of novel technologies on the energy efficiency of steam cracking furnaces, computational fluid dynamics (CFD) simulations offer a lot of insight into the system hydrodynamics. As a part of the IMPROOF project various novel technologies will be installed on an industrial scale. Since the experimental measurements performed on the industrial scale are rather scarce compared to CFD simulations where the temperature and concentration is known at each location, CFD simulations have become a crucial tool in process intensification. The experimental data gathered during the IMPROOF experiments will be used to validate and optimize the CFD models. The CFD models in turn can be used to further optimize the design.  
The focus of this deliverable D3.3 is to illustrate the furnace model developed at the Laboratory for Chemical Technology. This framework allows to perform simulations of the radiative side of gas-fired furnaces accounting for temperature and wavelength dependent emissivity.   

In this document, the application of Large Eddy Simulation (LES) to a steam-cracking furnace is described. The LES methodology was already reported in a previous Deliverable (D3.1), and specific developments as well as results are presented and analysed here. The objective was to demonstrate the feasability of LES of large size systems and to show the added value of this approach compared to other CFD methods (such as RANS).

Another objective was to evaluate the impact of high emissivity coating on the thermal behaviour of a furnace, by simulating the radiative heat transfer in the furnace taking into account the radiative properties of the treated wall surfaces.

B.  Cuenot et al. (CERFACS)

The objectives of the WP4 is to deploy the demonstrator at integrated commercial scale (TRL6) with the most effective technologies improving heat transfer of ethylene furnaces. In this report the operational conditions representative of the industrial environment are defined.   

The objectives of this report is to present the technologies that Dow will test at demonstrator scale (TRL6). In this report, the selected technologies are presented plus the criteria to implement some other technologies. 

The objectives of this report is to present the instruments that will be used to measure the performance gains of the TRL6 unit in Dow. Although the selected TRL6 furnace is equipped with some instruments, the current report explains that Dow executes a capital project to install additional instruments. These instruments are necessary to measure coking tendency, radiant coils heat transfer, measure and control energy efficiency. 

The objective of this report is to present the status of the TRL6 demonstration at the Dow commercial-scale units. The previous deliverables of WP4 illustrated how the selection of the furnace units and demonstration technologies was made. The current document shows the preliminary performance data of the reference and demonstration (TRL6) furnaces.
This report is intentionally divided into three separate evaluations. The first part illustrates the analysis as carried out by Dow. The second part presents the analysis carried out by AVGI.
The third part presents the analysis carried out by Technip Energies.

This report assesses whether it is possible to improve the energy efficiency of steam cracking furnaces by at least 20%, and this in a cost- effective way, while simultaneously reducing emissions of greenhouse gases and NOx per ton ethylene produced with at least 25%.
To meet this goal, Technip Energies did extensive research and filed a patent in June 2017 for the three high efficiency furnace configurations described and evaluated in this report:
Case 1: Air preheat
Case 2: Full oxyfuel combustion
Case 3: Partial oxyfuel combustion
Each of these cases meets the required project objectives on energy efficiency and emission of greenhouse gases and NOx. 

The task 4.6 and thus D4.7 Innovation Management Internal Benchmark covered the following aspects:  The strategy was to review and analyse the innovation management process of industrial partners CRESS, JZHC, DOW, TECHNIP, S+C, AVGI. The objective was to collect, benchmark and share non confidential practices and strengths in terms of innovation management in general and related to the project. AYMING used the diagnostic tools and models developed in the frame of INSEC FP7 funded project: http://platform.insec-project.eu.  
More specifically, the study included the following aims:  
-To measure the level of maturity and performance of innovation process of partners regarding the INSEC referential   
-To obtain a collective analysis of the consortium regarding innovation management. Sharing best practices when this is possible regarding confidentiality aspects  
-To identify and select key modules to be implemented in order to improve the performance  
-To identify external tools and methodologies that enable implementation of the modules to the benefit of the company and IMPROOF project. 

This work presents an overview of the state of the art of olefin production in steam cracking furnaces and discusses various currently existing furnace technologies, as well as their expected future progress.
This research aims at identifying:
key parameters that affect the performance and economics of steam cracking furnaces
areas for improving the economics and performance of the furnace
novelties in steam cracking furnaces for increasing energy efficiency and reducing greenhouse gas emissions
benefits and industrial challenges of the new technologies for furnace improvements.

 This report evaluates the potential benefit that the technologies being studied within the IMPROOF project can bring to a cracking furnace. In this context, benefit has been quantified as the additional annual production of ethylene and propylene, compared to a base case.  
The evaluation has been carried out by means of COILSIM1D simulations of a propane cracking furnace, modelled following the geometric parameters and operating conditions that have been provided by Dow, to ensure that the values given to the model as input are representative of what can be expected in a CUP furnace, i.e. the unit that will be used for demonstration of the technologies in the project.  
Besides a base case, which has been used as a benchmark for comparison, 20 additional scenarios have been simulated, evaluating the individual impact of Emisshield®, HT-E, SCOPE® and SFT®. Combinations of these technologies were also simulated, and one additional case evaluates the impact of using pure oxygen instead of air as oxidizer in the furnace.  
The highest benefit was calculated for the cases that consider a coil entirely made of HT-E material, with SFT® or SCOPE® geometries, placed inside an Emisshield®coated furnace. These configurations led to an additional annual production of ethylene and propylene of about 1.3 KTA (+3.3%) when compared to the base case. 

The purpose of Task 5.3, summarised herein as Deliverable 5.4, is to examine the operating data from the demonstration furnace (1BA111), and then benchmark against the results of the simulations carried out  in Task 5.2, and reported as Deliverable 5.3. Depending on the agreement between simulation, experimental and field measurements, the simulations can be adjusted, so as to better capture and assess the impact of the investigated developments in the project. 
In fact, the results have been reinforced by the operating data and the simulation tool, COILSIM1D, has been validated. Kinetic, single event microkinetic models, reactor models, radiant box models and convection section models have been shown to provide reliable estimates for further use in Task 5.4. 
The benefits have been quantified as the additional annual production of high value chemicals; the extension of run-length; the reduction in fuel consumption; and ultimately, the reduction in direct CO2 emissions from the furnace stack. All technologies have been evaluated relative to a base case of an unmodified, so-called reference furnace (1BA104). 
After the validation exercise, additional scenarios have been simulated for the individual and combined impact of: Emisshield® refractory wall coating, HT-E® Al-rich coil material, SCope® and SFT® 3D coil geometries, a novel furnace design (referred to variously as ‘TRL-9' and ‘Low-Emission Furnace'), oxyfuel combustion with flue gas recycle, and the use of biogas fuel. 
The greatest benefit was calculated for the case that considers a coil entirely made of HT-E alloy, with 3-D geometry applied to the last pass, placed inside an Emisshield®coated furnace. Such a configuration leads to an additional annual production of high value chemicals of about 46.328 KTA (+1.92%) when compared to the base case and 0.6% reduction in furnace firing rate (and therefore, direct CO2 emissions). 

This document describes the methodology and the results from Life Cycle Assessment (LCA); Life Cycle Costing  (LCC); and analysis according to the Greenhouse Gas Protocol (GHG Protocol) of the technologies identified in Task 5.3. These technologies are designed to reduce  both the energy demand of and the carbon and nitrogen emissions from cracking furnaces.
LCA calculates the environmental impact of the whole production cycle of a given product and identifies potential hotspots and avoids burden shift. Hence, LCA characterizes the product as whole, including raw materials and utilities involved in its production. The so-called ‘cradle-to-gate' system boundary has been chosen because it is a common approach in the base chemicals industry. All results are normalised to one mass unit of High Value Chemicals (HVCs) exported from the separation train (the ‘gate').
Six technologies have been considered:
Emisshield® high-emissivity coating
Novel Al-rich coil alloy HT-E
3D Reactor Geometries: SCope® and SFT®
Oxyfuel combustion with flue gas recycle
Technip Energies patented furnace arrangement (referred to as ‘TRL9' or ‘LowEmission Furnace)
Biogas combustion
The reference Dow CUP furnace is the baseline. Ten additional scenarios, both hypothetical, and currently being tested on the demonstration furnace, as well as three sensitivity studies, have been chosen for comparison. All input parameters for LCA and LCC are from full furnace COILSIM1D simulations validated as described. The methodology, results and validation are described in Deliverable 5.4.
LCA shows that propane feed has a major impact on the environmental footprint: ~ 65% carbon footprint for the baseline which downscales the impact of IMPROOF solutions. With a narrower view (Scope 1 emissions, GHG Protocol) the proportional impact of IMPROOF technologies increases allowing up to 67% reduction of greenhouse gas emissions by oxyfuel furnace with an integrated carbon capture and storage system. SFT® 3D coils combined with HT-E coil alloy and Emisshield ® refractory wall coating gives the best TRL6 result, reducing the carbon footprint by 0.53% (through LCA study). Economic-wise it has little impact (0.068% increase in profit margin) unless carbon pricing is applied. The study shows that the more radical changes described below are needed to achieve the project goals.
The most effective solutions for tackling climate change are, then: biogas combustion (up to 40% reduction in overall carbon footprint of HVCs); TRL9/Low-Emission Furnace with combustion air preheat and carbon neutral electricity grid (21.7% reduction); and, finally, oxyfuel combustion with carbon capture and storage (23% reduction). Such cases depend on certain key assumptions such as, for example, the type of oxygen source (for oxyfuel), and the fraction of renewable sources supplying the electricity grid
(for TRL9). Sensitivity studies quantifying such effects are presented in the document.  

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