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SPINE LCI dataset: Production of methylene diphenyl diisocyanate, MDI (APME)

Administrative

Technical System

System Boundaries

Flow Data

About Inventory


Administrative
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Finished Y

Date Completed 1999

Copyright APME

Availability Public


Technical System
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Name Production of methylene diphenyl diisocyanate, MDI (APME)

Functional Unit
(see also Functional Unit Explanation)
1 kg MDI - Methylene diphenyl diisocyanate

Process Type Cradle to gate

Site Europe

Sector Materials and components

Owner Europe

Function The information given below comprises all available information in the datasheet from APME, from which this data set is acquired. All flows have been followed to the cradle. However, only the main production process is been described here.

MDI, methylene diphenyl diisocyanate, is one of the precursors used in the production of polyurethanes.

MAIN PROCESS:
1. Extraction of crude oil
2. Oil refining
3. Benzene production
4. Nitrobenzene production
5. Aniline production
6. MDA (methylene dianiline) production
7. MDI production

SUB PROCESSES:
a. Production of sulphur and sulphuric acid, to be used in the production of nitrobenzene
b. Production of hydrogen for the aniline production.
c. Production of methanolo from natural gas - production of formaldehyde from the methanol. The formaldehyde is used for the MDA production.
d. Production of ammonia from natural gas. The ammonia is used fro the benzene production. The ammonia is also used to produce nitric acid, which is used in the production of nitrobenzene.
e. Production of phosgene from carbon monoxide and chlorine. The carbon monoxide is produced from coke/natural gas. The chlorine is produced from sodium chloride. The phosgene is used from the MDI production step.

The inputs to the process are crude oil, natural gas, sulphur, coke/naturalgas, sodium chloride and the by-product sulphur dioxide.

For raw materials, inputs as listed from APME, have been recorded in this data set. For ’’Fuels & Feedstocks’’, all fueltypes have been included. In addition, ’’Total Energy’’ for ’’Hydro’’, ’’Nuclear’’ and ’’Recovered Energy’’ fueltypes from ’’Primary Fuels & Feedstocks’’ have been included. ’’Recovered Energy’’ has been recorded in this data set as an outflow with positiv sign. For ’’Water Use’’ the total amount has been recorded.



System Boundaries
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Functional Unit Explanation
(see also: Functional Unit)
MDI, methylene diphenyl diisocyanate, is one of the precursors used in the production of polyurethanes. There are five main areas of use for polyurethanes: the furniture and mattress sector, the automotive industry, the consumer sector, the building industry and the

Nature Boundary ’’The data presented in the result tables are simply a listing of the data for which information is available’’. Especially for air and water emissions, the magnitude of many of the parameters often depends on the degree of monitoring of the parameter, since a company which does not monitor the parameter, may have been estimated it instead.

The categories used to identify the different emissions or groups of emissions are empirical and reflect the ability of the many plants to identify specific emissions. For instance, methane, aromatic hydrocarbons and polycyclic hydrocarbons have been identified as separate groups, while the more general name hydrocarbons has been reserved for the remainder. However, some companies may not have reported all of the emissions separately. Therefore, the category metals, for example, may include some metals which were specifically identified by other companies and are included under the specific names elsewhere in the tables. Double-counting has been avoided. However, some of the emissions included separately may have contributed to the BOD and COD values.

Generally, the emissions to air and water recorded are those remaining after any on-site air or water treatment.

Time Boundary Data refer to the year 1995-1996. Data for upstream production of fuels and raw materials are probably from the same time, or somewhat older.

Geographical Boundary European average data. Data were supplied from 5 producers in Belgium, Germany, Italy and the Netherlands.

For the APME Eco-profiles in general, the coverage of European production varies from 60 to 100% depending upon the product, although this may not be true for some of the intermediates (including toluene). For some intermediates, with the exception of chlorine, sodium hydroxide and electrolytic hydrogen, the average data might not be truly representative of the European average for their production.

The values of some of the parameters reflect the country in which the plants are located. For example, plants in countries where much of the electricity is generated from coal, tend to exhibit higher emissions of sulphur oxides than plants in other countries.

Other Boundaries The following excluded subsystems are explicitly mentioned in the Methodology report:
- External incineration of waste and external recycling. Other external waste treatment is, most likely, also excluded, as concluded by the way solid waste is classified. (On-site waste incineration, on the other hand, is included).
- Energy consumption and emissions caused by operating personnel: consumption of food and car transports to work. Both were considered to be small compared to the totals.
- Capital equipment and buildings, with two exceptions: road transport and oil well operation. In these two cases, construction and maintenance have been included. In most cases, the lifetime of the plants is sufficiently long to allow exclusion of capital equipment and buildings, which typically contribute <0,01% to the totals.

No cut-off criteria for exclusion of minor inputs and outputs are stated. However, in the Metholodogy report, a general recommendation is given that it is important to demonstrate that the contribution of an ancillary material to the overall system is negligible, rather than simply assuming it to be negligible because of its small mass.

European average data. Results are based on data supplied by 5 MDIproduction plants in 4 countries: Belgium, Italy, Germany and the Netherlands. Their total production was 557,000 tonnes.

Allocations In the Methodology report and the different ’’Eco-profiles...’’ reports, the following co-product allocations are mentioned:

- Extraction of crude oil and natural gas: For the North Sea oil rigs, the flare losses and the own-use data have been spread over all of the saleable products on the basis of their calorific values.
- Refineries: Inputs and outputs have been partitioned over all usable or saleable refinery products on a simple mass basis.
- Crackers: Most likely, this also applies to the products from the crackers: ethylene, propylene, butenes etc.
- Chlorine plant (electrolysis of sodium chloride): Stoichiometric allocation of sodium chloride and some other inputs and outputs has been applied to the three products: chlorine, sodium hydroxide and hydrogen. Care was taken to attribute inputs or outputs only to the products which derive benefit from these inputs or outputs. E.g. sulphuric acid is used as a drying agent for chlorine, therefore, the sulphuric acid input should be attributed to chlorine only. Electricity was partitioned on all products on a simple mass basis.
- Sulphuric acid: 98% sulphuric acid is widely used as a drying agent. Often, the dilute acid leaving the system can be used as a reagent in other reactions. However, the dilute acid cannot simply be subtracted from the input acid. The energy needed to produce concentrated acid by removing water is attributed to the process.
- Hydrochloric acid by-product: In many reactions, chlorine is used as an oxidation or chlorination agent, which inevitably results in the formation of HCl as a by-product. Only the inputs and outputs associated with the production of the stoichiometric amounts of chlorine and hydrogen incorporated into the HCl have been assigned to the HCl.
- On-site steam and electricity: A primary energy equivalent corresponding to the steam energy, assuming 80% efficiency, was subtracted from the total energy input. The remainder was assigned to the electricity.

These allocations are general for data from APME, and only applicable for datasets where the above mentioned processes are included.

Systems Expansions Not applied.


Flow Data

General Activity QMetaData
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Date Conceived 1995-1996
Data Type Derived, mixed
Represents
Method European average data. Results are based on data supplied by 5 MDI production plants in 4 countries: Belgium, Italy, Germany and the Netherlands. Their total production was 557,000 tonnes.

Data were averaged over all plants and weighted by the production (mass) from each plant. Vertical averaging has been applied wherever there have been sufficient data from upstram raw material and fuel producers. In vertical averaging, each production sequence (i.e. each plant + its specific suppliers) is calculated separately, and the final result is the average of the results from the individual production sequences weighted by the output from each production sequence (plant). Horizontal averaging has, however, been applied for some processes over which the producers have no control and data from a specific supplier were not available. In these cases, European average data from the other participants or suppliers were used in the calculations.

According to the APME methodology report, the amounts of combusted fuels have been corrected by adding the feedstock (gas and oil) residues used as fuel within the processes, before calculating the CO2 emission.

For fuels and feedstock materials, actual gross calorific values (energy content) have been used in the calculations. Typical values: 45,0 MJ/kg for crude oil, 38,8 MJ/m3 (54,1 MJ/kg) for natural gas, 28,0 MJ/kg for coal, 15,0 MJ/kg for lignite, 9,3 MJ/kg for sulphur.

Data from APMEs website www.lca.apme.org have been downloaded as exe-files. The files are opened and imported into Microsoft Excel. Further, the data from MS Excel is exported to a MS Access database.

Literature Reference
APME - Association of Plastics Manufacturers in Europe, website:
http://lca.apme.org

Notes For raw materials, inputs as listed from APME, have been recorded in this data set. For ’’Fuels & Feedstocks’’, all fueltypes have been included. In addition, ’’Total Energy’’ for ’’Hydro’’, ’’Nuclear’’ and ’’Recovered Energy’’ fueltypes from ’’Primary Fuels & Feedstocks’’ have been included. ’’Recovered Energy’’ has been recorded in this data set as an outflow with positiv sign. For ’’Water Use’’ the total amount has been recorded.

See Notes in Inventory for a list of how the nomenclature for substances used by APME have been translated into the nomenclature used by CPM (CPM 2000:2). The Nomenclature for FlowTypes has in some cases been changed:
Old name:
Resources
New name:
Natural resource
Old name:
Waste
New names:
Residue
Old name:
Co-product
New name:
By-product

Although the dataset contains a large number of decimals, which usually implies that there is a great accuracy in the data, we are somewhat questioning about this accuracy.

Flow Table and Specific Meta Data
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QMetaData Direction FlowType Substance Quantity Min Max SDev Unit Environment Geography

Input Natural resource Air 420848.4321 mg Air Europe

Input Natural resource Barytes 182.313477 mg Ground Europe

Input Natural resource Bauxite 215.1070064 mg Ground Europe

Input Natural resource Bentonite 98.8626278 mg Ground Europe

Input Natural resource Biomass 4308.016196 mg Ground Europe

Input Natural resource Calcium sulphate 9.84150952 mg Ground Europe

Input Natural resource Chalk 1.16E-23 mg Ground Europe

Input Natural resource Chromium in ore 0.000000701 mg Ground Europe

Input Natural resource Clay 10.96847121 mg Ground Europe

Input Natural resource Crude oil 498519.2564 mg Ground Europe

Input Natural resource Dolomite 43.29015072 mg Ground Europe

Input Natural resource Feldspar 1.47E-29 mg Ground Europe

Input Natural resource Ferromanganese 0.594445828 mg Ground Europe

Input Natural resource Fluorite 3.222470165 mg Ground Europe

Input Natural resource Granite 0.0239 mg Ground Europe

Input Natural resource Gravel 2.224645389 mg Ground Europe

Input Natural resource Hard coal 321096.3224 mg Ground Europe

Input Natural resource Hydro energy 0.504996345 MJ Ground Europe

Input Natural resource Iron in ore 697.2895183 mg Ground Europe

Input Natural resource Lead in ore 1.824228531 mg Ground Europe

Input Natural resource Lignite 101969.6316 mg Ground Europe

Input Natural resource Limestone 20036.78997 mg Ground Europe

Input Natural resource Metallurgical coal 17769.63378 mg Ground Europe

Input Natural resource Natural gas 1097357.656 mg Ground Europe

Input Natural resource Nickel in ore 0.109593303 mg Ground Europe

Input Natural resource Nitrogen 127041.4279 mg Ground Europe

Input Natural resource Nuclear energy 5.51299683 MJ Ground Europe

Input Natural resource Olivine 5.963022144 mg Ground Europe

Input Natural resource Oxygen 150086.3185 mg Ground Europe

Input Natural resource Peat 369.2391523 mg Ground Europe

Input Natural resource Phosphate 7.208932294 mg Ground Europe

Input Natural resource Potassium chloride 12882.51663 mg Ground Europe

Input Natural resource Rutile 1.67E-23 mg Ground Europe

Input Natural resource Sand 821.4974124 mg Ground Europe

Input Natural resource Shale oils 27.86131345 mg Ground Europe

Input Natural resource Sodium chloride 471493.8802 mg Ground Europe

Input Natural resource Sulphur 4905.315648 mg Ground Europe

Input Natural resource Sulphur (bonded) 2441.899215 mg Ground Europe

Input Natural resource Water, cooling 276402200.6 mg Water Europe

Input Natural resource Water, process 84124967 mg Water Europe

Input Natural resource Wood 806.4279906 mg Ground Europe

Input Natural resource Zinc in ore 0.0571 mg Ground Europe

Output Co-product Recovered energy 4.627478011 MJ Technosphere Europe

Output Emission 1,2-Dichloroethane 0.000026 mg Air Europe

Output Emission Acid as H+ 42.0974748 mg Water Europe

Output Emission Al 8.415284821 mg Water Europe

Output Emission Aldehydes 1.562200034 mg Air Europe

Output Emission As 0.00028 mg Water Europe

Output Emission BOD5 814.8387071 mg Water Europe

Output Emission Ca2+ 112.5958223 mg Water Europe

Output Emission CFCs 2.894967239 mg Air Europe

Output Emission Chloroorganics 12.15327877 mg Air Europe

Output Emission Chloroorganics 3.297053857 mg Water Europe

Output Emission Cl- 142499.5935 mg Water Europe

Output Emission Cl2 0.602185536 mg Air Europe

Output Emission Cl2 11.16844301 mg Water Europe

Output Emission CN- 0.0135 mg Water Europe

Output Emission CO 2796.799443 mg Air Europe

Output Emission CO2 3382476.452 mg Air Europe

Output Emission CO32- 147.4355949 mg Water Europe

Output Emission COD 5347.148016 mg Water Europe

Output Emission CrO3 0.000000843 mg Water Europe

Output Emission CS2 0.000249 mg Air Europe

Output Emission Cu 0.161499042 mg Water Europe

Output Emission Dissolved organics 329.9612663 mg Water Europe

Output Emission Dissolved solids 8186.706777 mg Water Europe

Output Emission F- 0.00375 mg Water Europe

Output Emission F2 0.00275 mg Air Europe

Output Emission Fe 1.879585663 mg Water Europe

Output Emission H2 1800.721572 mg Air Europe

Output Emission H2S 0.517099001 mg Air Europe

Output Emission H2SO4 15.91785856 mg Air Europe

Output Emission HCl 134.9068456 mg Air Europe

Output Emission HCN 5.71E-29 mg Air Europe

Output Emission HF 6.030281778 mg Air Europe

Output Emission Hg 0.321388128 mg Water Europe

Output Emission Hg 0.406742106 mg Air Europe

Output Emission K+ 369.3147008 mg Water Europe

Output Emission Metals 234.1358744 mg Water Europe

Output Emission Metals 6.838957934 mg Air Europe

Output Emission Methane 17825.51088 mg Air Europe

Output Emission Mg 14.6599637 mg Water Europe

Output Emission N total 63.39169854 mg Water Europe

Output Emission N2O 0.127884205 mg Air Europe

Output Emission Na 95871.52424 mg Water Europe

Output Emission NH3 40.64987605 mg Air Europe

Output Emission NH4+ 204.5531643 mg Water Europe

Output Emission Ni 7.628218187 mg Water Europe

Output Emission NO3- 153.6808522 mg Water Europe

Output Emission NOx 15085.24156 mg Air Europe

Output Emission Oil 38.82394019 mg Water Europe

Output Emission Other organics 158.5275045 mg Water Europe

Output Emission Particles 4734.127239 mg Air Europe

Output Emission Pb 0.000199 mg Air Europe

Output Emission Pb 0.000469 mg Water Europe

Output Emission Phenol 4.824860716 mg Water Europe

Output Emission PO43- 9.440771951 mg Water Europe

Output Emission S2- 0.697170589 mg Water Europe

Output Emission SO2 14587.96741 mg Air Europe

Output Emission SO42- 6073.240307 mg Water Europe

Output Emission Suspended solids 2331.729683 mg Water Europe

Output Emission Thiols 0.0726 mg Air Europe

Output Emission Vinyl chloride 2.18E-26 mg Water Europe

Output Emission Vinyl chloride 0.0000259 mg Air Europe

Output Emission VOC 39.02861248 mg Water Europe

Output Emission VOC 3989.291933 mg Air Europe

Output Emission VOC 63.49293054 mg Air Europe

Output Emission VOC, aromatic 72.55037345 mg Air Europe

Output Emission Zn 51.32797735 mg Water Europe

Output Product MDI (methylene diphenyl diisocyanate) 1 kg Technosphere Europe

Output Residue Construction 78.34316035 mg Ground Europe

Output Residue Industrial 10519.78445 mg Ground Europe

Output Residue Inert chemical 2840.631442 mg Ground Europe

Output Residue Metals 14.77700161 mg Ground Europe

Output Residue Mineral 83807.13934 mg Ground Europe

Output Residue Paper 4.871958434 mg Ground Europe

Output Residue Plastics 162.4004846 mg Ground Europe

Output Residue Regulated chemical 4662.541479 mg Ground Europe

Output Residue Slags & ashes 20716.44427 mg Ground Europe

Output Residue To incinerator 1662.112905 mg Technosphere Europe

Output Residue To recycling 366.8777036 mg Technosphere Europe

Output Residue Unspecified 11.89029197 mg Ground Europe

Output Residue Wood waste 7.939058986 mg Ground Europe


About Inventory
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Publication ’’Eco-profiles of the European plastics industry’’, report for MDI. ’’Eco-profiles of plastics and related intermediates: Methodology’’, I. Boustead, The European Centre for Plastics in the Environment of The Association of Plastics Manufacturers in Europe (APME), Brussels, 1999. Reports are available at APME’s web site http://lca.apme.org. ------------------------------------------------------------ Documented by Caroline Sjöberg and Sofia Haargaard, Volvo Technological Development Documentation reviewed by: Ann-Christin Pålsson, IMI, Chalmers University of Technology Published in SPINE@CPM: 3 April 2002 ------------------------------------------------------------

Intended User 1. APME member companies
2. L

General Purpose The general purpose of the study was to demonstrate the commitment of APME (Association of Plastics Manufacturers in Europe) to improve the environmental impact of the processes, from extraction of oil to granulate or polymer compound.

Detailed Purpose Eco-profiles are intended primarily as buiding blocks for use in the construction of complete life cycle analyses.

1. Provide APME member companies with information which will highlight potential areas for improving manufacturing processes

2. Provide valuable inventory data for downstream users of plastics, such as packaging manufacturers, who will be able to produce their own eco-balance assessments (i.e. LCAs) of individual products.

Objectives and areas of application for the Eco-profiles:
- Plastics waste management studies
- Internal company benchmarking
- Product development. Detailed environmental information to customers of APME members for use in improving the overall environmental performance of products and systems.
- Ensuring that the data are neutral.

The purpose of the 1999 update was to re-issue all of the data sets together using the latest data available and with all of the results forming a consistent data set. Significant technological and commercial changes have occured since 1989-93, the period to which the oldest group of Eco-profile data referred. Also the quality of data reported by the companies has improved since then.

Commissioner

Practitioner Boustead, Ian.

Reviewer Not available

Applicability The data are applicable to both MDI monomer and polymer; differences between the two have been found to be insignificant.

European average data. Results are based on data supplied by 5 MDI production plants in 4 countries: Belgium, Italy, Germany and the Netherlands. Their total production was 557,000 tonnes.

The data are calculated on a cradle to gate basis, therefore, nuclear power, coal, limestone etc should be regarded as resources from environment, i.e. no supplier activities should be connected to these flows.

Remember that, in an LCA, two systems could only be compared if they perform equivalent functions. For instance, production of 1 kg of polyethylene should not be compared directly with production of 1 kg of polycarbonate. Only in a specific application, a comparison between the two materials could be meaningful.

It is not reported how large differences there are between different producers with respect to emissions and other environmental impacts. Therefore, it is also not known how well the data could represent production at a specific plant.

About Data European average data for MDI production on a cradle to gate basis, issued by APME (Association of Plastics Manufacturers in Europe), and produced in association with the independent expert I. Boustead. The companies participating in the project have supplied data on the chemical processes. Data are probably fairly representative for production of MDI in Europe. However, the reliability of the data depends on the quality of the records maintained by the individual companies. Mass and energy balances have been checked, and the details of all calculations were referred back to individual companies for checking before being incorporated into the final averages.

Data for supporting operations and transport have been obtained from other manufacturers and operators as part of an on-going exercise involved in maintaining an LCI database. The quality of data for public electricity production is not described. However, it is stated that information on the production of fuels and energy have been derived from the reports of the International Energy Agency 1996, which contain data for 1995. No other process data have been derived from the literature.

The accuracy of data for materials and energy supplied by companies is considered to be about 5-10%. Wastes and emissions are often measured with less accuracy. Even for a regulated emission, the procedure for measuring and reporting is usually based on sampling rather than continuous monotoring. The accuracy is often unknown.

Vertical averaging has been applied wherever there have been sufficient data from upstream raw material and fuel producers.

In vertical averaging, each production sequence (i.e. each plant + its specific suppliers) is calculated separately, and the final result is the average of the results from the individual production sequences weighted by the output from each production sequence (plant). Horizontal averaging has, however, been applied for some processes over which the producers have no control and data from a specific supplier were not available. In these cases, European average data from the other participants or suppliers were used in the calculations.

For fuels and feedstock materials, actual gross calorific values (energy content) have been used in the calculations. Typical values: 45,0 MJ/kg for crude oil, 38,8 MJ/m3 (54,1 MJ/kg) for natural gas, 28,0 MJ/kg for coal, 15,0 MJ/kg for lignite, 9,3 MJ/kg for sulphur. The following degrees of efficiencies have been used to convert electricity production in nuclear plants and hydro plants, respectively, to primary energy equivalents: 35% for nuclear electricity, 80% for hydro electricity.

According to the APME methodology report, the amounts of combusted fuels have been corrected by adding the feedstock (gas and oil) residues used as fuel within the processes, before calculating the CO2 emission. CO2 emission values have been calculated from the composition of the fuel, assuming complete combustion: CO2 emission = 3,67 x {mass fraction of carbon in fuel}/{calorific value in MJ/kg} (kg/MJ fuel).

Notes The following substance names have been changed from the nomenclature used by APME to adapt to nomenclature according to CPM report 2000:2.

RESOURCES

Old name New name
Barite (Ba(SO4) Barytes
Bauxite (Al2O3*H2O) Bauxite
Chromium (Cr3+, Cr6+) Chromium
Coal, hard unspecified Hard coal
Gravel (unspecified) Gravel
Hydro (primary energy) Hydro energy
Olivin (unspecified) Olivin
Phosphate (as P2O5) Phosphate
Potassium chloid Potassium chloride
Sand (unspecified) Sand
Sulphur (elemental) Sulphur
Wood (unspecified) Wood

EMISSIONS

Old name New name
Aluminium ion Al
Ammonium ion NH4+
Carbon disulfide CS2
Carbonate CO32-
Chlorine Cl2
Chromium oxide CrO3
Copper (Cu+) Cu
Ethane, 1-,2-, chloro 1,2-Dichloroethane
Fluorine (F2) F2
Hydrocyanic HCN
Hydrogen H2
Iron, Fe2+, Fe3+ Fe
Mercaptans Thiols
Metals (unspecified) Metals
Nickel ion (Ni++) Ni
Nitrate (NO3) NO3-
Oils (unspecified) Oil
Organo-Cl Chloroorganics
Other organics VOC
Particulates (unspecified) Particles
Sulfuric acid H2S4
Vinylchloride Vinyl chloride
VOC (hydrocarbons) VOC
VOC (hydrocarbons, oil) VOC
VOC (unspecified origin) m.fl. VOC
Zinc, ion (Zn++) Zn
Ni (Ni++, Ni3+) Ni

SPINE Data Report
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