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Substance Flow Analysis of Resorcinol

3 Turnover of resorcinol in Denmark

3.1 Statistical information
   3.1.1 Statistics Denmark
   3.1.2 The Danish Product Register
   3.1.3 The SPIN Database
   3.1.4 Discussion of statistical information sources
3.2 Survey information
   3.2.1 Glue industry
   3.2.2 Adhesives/bindings agents in the rubber industry
   3.2.3 Hair dye products
   3.2.4 Chemical industry
   3.2.5 Pharmaceutical industry
   3.2.6 Plastics industry
   3.2.7 Discussion of survey information
3.3 Summary and discussion

The turnover of resorcinol in Denmark is estimated by using available statistical information and by surveys of the industries where the major consumption is assumed to take place.

3.1 Statistical information

3.1.1 Statistics Denmark

There is no record of production of resorcinol in Denmark and there has not been registered any sale of goods containing resorcinol in Denmark between 1995 and 2003 (Statistics Denmark, 2003).

The following data presents the available import and export statistics for resorcinol (defined as KN code 2907 2100 “Resorcinol and its derivates”) (Statistics Denmark, 2003).

Table 3.1. Import and export of resorcinol to/from Denmark in 1994-2002.

Table 3.1 shows there are large variations in the import and export of resorcinol to/from Denmark. The export generally seems to be significantly smaller than the import and the last years there have been little or no export of resorcinol.

It should be noted that the data from Statistics Denmark includes derivates of resorcinol, and the import of pure resorcinol may accordingly be much less than the figures listed in the table. There exists between 10 to 20 derivates of resorcinol that may all be included in the import and export figures. Some of the most important derivates are listed below.

• Resorcinol Dibenzoate
• β-Resorcylic Acid
• g-Resorcylic Acid
• Resorcinol Dimethyl Ether
• 4-Acetylresorcinol
• Halogenated Resorcinol
• 4,6-diaminoresorcinol
• Resorcinol Monobenzoate
• Thio-bis-resorcinol
• Resorcinol Monoacetate
• 3,4'-Diaminodiphenylether
• Dihydroresorcinol
• Hydroxyethyl Ether of Resorcinol
• Resorcinol Diglycidyl Ether
• Resorcinol Dioxyacetic Acid
• Benzophenone
• Di-t-butylresorcinol
• m-Aminophenol

The distribution between resorcinol and resorcinol derivates in the import/export figures from Statistics Denmark are unknown and the exact import/export of resorcinol can thus not be determined. A range for the import of resorcinol in year 2002 can in principle only be estimated to be between 0 kg and 10098 kg.

3.1.2 The Danish Product Register

To obtain a cross reference on the import and export figures from Statistics Denmark, the amount of products containing resorcinol has been investigated based on data form the Danish Product Register (PR). It is the notifying companies alone that are responsible for updating in PR. The companies are obliged to send in any relevant information about changes regarding their notified products. Table 3.2 below summarises the compiled information.

Table 3.2. Number of product types and their content of resorcinol.

The most frequent industrial sectors consuming resorcinol are described briefly in Chapter 2.

It is emphasized that the PR contains data for active as well as non-active products on the Danish market. If a product is not active anymore – or the amounts being imported or produced changes, the notifying company is responsible for giving this information to the PR. However, experience shows that this is not always the case and in practice, the amounts may be both larger and smaller.

Another uncertainty in the information from the PR is that there must be more than three products within a given category in order to be included in the information that the PR is allowed to reveal to the public. In theory, there can thus be a large amount of resorcinol in one or two products with a content between 20 and 50%.

3.1.3 The SPIN Database

SPIN – Substances in Preparations In the Nordic countries – is a database that contains “non-confidential” information on substances from each of the Nordic product registers.

The intention behind the database SPIN is to make available to the public as much data as possible from the registers. Secrecy rules as in the Product Register can then be overcome by aggregation of the data from each register. Thereby, the number of products within a certain use or industry category is increased. The information included is for example the number of products containing the substance, the annual tonnage, industrial categories and use categories, the annual tonnage within these categories and the presence or absence of the substance in consumer products.

Information in the SPIN database shows that in 2000, a total amount of 23.6 tons of resorcinol was used in 30 preparations. In 2001, the total use was 23.5 tons in 31 products.

The SPIN database also shows that in Denmark resorcinol is used in the manufacture of rubber, plastic, machinery and equipment. In the other Nordic countries resorcinol is also used in the manufacture of products of wood and cork, luggage, handbags, saddlery, harness and footwear, chemicals and chemical products. The typical functions of resorcinol in these products are as adhesives/bindings agents, hardeners, catalysts/process regulators, pharmaceuticals, dyestuff/pigments and intermediate (SPIN, 2003).

The SPIN database also provides a quantitative distribution of the amounts of resorcinol on different use categories and EU's Nomenclature of economic activities (NACE). However, only a limited number of products are included in this overview.

Table 3.3 below summarises the compilation of information regarding Denmark from the SPIN database for the years 2000 and 2001.

Table 3.3. Number of products and amounts of resorcinol distributed on use categories (UC62 and national) and NACE-codes

The SPIN database only shows non-classified information. This means that each category must contain at least four products from at least three different companies in order to be included. If this criteria is not fulfilled the data will not be available. This explains why the presented data from the SPIN database is only a subset of the data from the Danish Product Register. More products are shown within the use categories (UC62) compared to the use categories (national) and the NACE categories. The reason is that the categories within (UC62) are broader defined than the other categories. Products may be registered in more than one category. This means that the 5.9 tons of hardeners registered in year 2000 may also be included in the 19.8 tons of adhesives registered in year 2000. Hence, it is not possible to obtain the total consumption be adding the tonnage from each category.

3.1.4 Discussion of statistical information sources

The information from the Danish Product Register can be combined with data from the SPIN database. According to SPIN, there were in 2001 registered 31 different products being imported and used for industrial purposes in Denmark, in total representing 23.5 tonnes of resorcinol. In 2000 there were 30 different products, in total representing 23.6 tonnes. These figures are very similar to the information obtained from the Danish Product Register, giving a total of 23 tons of resorcinol.

However, both the Product Register and the SPIN database gives figures for resorcinol import that are significantly higher – about a factor 2 - than the amounts reported by Statistics Denmark. This may be due to the differences in classification of products, e.g. it is not known whether the KN-code used for resorcinol and its derivates include resorcinol in formulations like wood glue.

It is concluded from the statistical information that the import and use of resorcinol for industrial purposes amounts to about 23 tons per year. As is shown in the following survey, there may however be an additional consumption that for one reason or another has not been included in the statistical information. The survey also indicates that the some of the amounts reported to the Product Register are not relevant in 2003, i.e. there may be an overregistration in the Product Register when compared to the use reported by industry.

3.2 Survey information

Due to the uncertainties associated with the statistical information, a survey among different industries was performed. The main purpose of the survey was to cross-check or verify the statistical information and if possible obtain more detailed information about the applications of resorcinol in Denmark. With this information better estimates of the potential for human exposure and dissemination in the environment can be established.

The survey covered the following industries.

• Glue industry
• Rubber industry
• Cosmetic industry
• Chemical industry
• Pharmaceutical industry
• Plastic industry

3.2.1 Glue industry

Resorcinol is a component in different wood glues and hardeners used for load bearing constructions and laminated wood constructions. The Danish Adhesives and Sealants Association contacted all relevant members for information about production and import of glues and hardeners containing resorcinol. A total of 11 companies were contacted and 10 responded to the survey.

No production of resorcinol-containing glue was reported by the respondents from the Danish Adhesives and Sealants Association. It is, however, remarked here that 751 kg of resorcinol was imported for glue and adhesive manufacturing in the paintmaking industry and this figure is included in the overview for the glue industry. The total import and production of resorcinol in wood glue is estimated to be between 3.4 and 11.6 tons, see Table 3.4 for details.

Table 3.4. Survey of imports of resorcinol and resorcinol-containing glues for wood products.

3.2.1.1 Fate of resorcinol in wood glue
All wood glue is assumed to be used in production of load bearing wood construction and in high-quality plywood. This assumption has not been investigated further, e.g. by a survey of the wood industry.

When used as a glue in wood production, resorcinol will be strongly bound in a matrix, and the emissions of resorcinol from the product are assumed to be insignificant.

The ultimate fate of wooden products in Denmark is assumed to be incineration with energy recovery. The content of resorcinol does in this respect not change the classification of wood products as being suitable for incineration (Kvist et al., 2000).

3.2.2 Adhesives/bindings agents in the rubber industry

Resorcinol is used in the rubber industry as a bonding agent or primer to obtain good adhesion and facilitate coating of fabric with latex, e.g. on cords, tires and mechanical rubber goods like conveyer belts and V-belts.

Worldwide, typical processes involve the use of RFL-dip (a solution of resorcinol (40%), formaldehyde and latex.

In the cord treatment process, a nylon, polyester or aramid cord is unwound from spools and directed into a solvent-based isocyanate primer, followed by flash-off in a hot air oven. The applied primer prepares the cord for the next step, a water-based resorcinol-formaldehyde latex (RFL) primer dip, that creates bonding sites on the cord. Subsequently, the RFL dip is dried by passing the cord through heated oven zones. The last coating operation involves dipping the cord in a solvent-based rubber adhesive tank and finally, the solvent in the adhesive is removed via an evaporation tunnel and the coated cord is spooled (USEPA, 1998). A typical RFL-dip (Bayer Vulkadur T) consists of pre-condensed resorcinol-formaldehyde resin, 40% aqueous solution.

Wall components and other segments of hoses, belts and tires are fabricated from fabric coated by using dip and dough spreading techniques. The types of fabrics used in these processes include cotton, cotton/polyester blends, nylon, polyester/nylon, and aramid.

RFL-dip is also used for coating of metal with rubber. No information regarding the processes used for such applications has been found in the project.

A survey of 14 Danish companies producing a wide range of rubber products revealed that only one company uses resorcinol-containing adhesives in the manufacturing of conveyer belts and V-belts. In the process, small pieces of non-vulcanised rubber are dissolved in the resorcinol solution. The non-vulcanised rubber/resorcinol mixture is used as an adhesive to fasten pieces of for example conveyer belts before they are vulcanised. The adhesive is applied manually with a brush in small amounts. It is estimated that 0.1 gram of resorcinol compound is used per kilo final product. The annual amount of resorcinol-containing adhesive being imported amount to 1300 kg, of which 20% - or 260 kg – is resorcinol.

3.2.2.1 Fate of resorcinol in rubber adhesives
After the products have been applied to the conveyer belt the resorcinol will be bonded in a strong matrix and it is assumed that no emissions during the use phase of such products will take place.

The ultimate fate of conveyor belts and V-belts (e.g. for automobiles) is either recycling, incineration with energy recovery or land filling. Recycling is not very likely, because conveyor belts are based on textiles. Incineration with energy recovery is possible, but requires that the belts are cut in sizes that are suitable for incineration. Land filling is also likely, e.g. following a shredding process where the whole conveyor belt is treated in a hammer mill, separating primarily metals from other materials. The metals can be recycled, whereas rubber, textile and plastics fractions are deposited in a landfill.

Rubber is not assumed to degrade significantly in a modern landfill and accordingly, the resorcinol will be bonded in the rubber matrix. When resorcinol is incinerated, it will mainly be broken down to CO2, CO, CH4, and NMVOC (Frydendal, 2003).

3.2.3 Hair dye products

Resorcinol is used as dyestuff in hair dye products. The Cosmetics Directive allows the use of resorcinol in concentrations up to 5%. According to The Association of Danish Cosmetics, Toiletries, Soap and Detergent Industries (SPT), the majority (98%) of the hair dye products contain less than 1% resorcinol, while the remaining contains 1-2% resorcinol. In a Danish investigation of hair dye products, resorcinol was found in 15 out of 18 products in concentrations from 0.002% to 1.13% (Rastogi, Worsøe & Jensen, 2003).

The magnitude of the consumption of resorcinol in Denmark was estimated by SPT using linear interpolation based on the consumption of resorcinol in the EU and the distribution in population:

Consumption of resorcinol in hair dye products in the EU: 90 tons (COLIPA, 2003).
EU population: 377.13 million (www.worldbank.org)
Danish population: 5.37 million (Statistics Denmark, 2003)
Danish share of EU population: 1.4%

Based on the above information, consumption of resorcinol in hair dye products in Denmark can be calculated to 1.28 tons

Similarly, the magnitude in the consumption in Denmark was estimated by linear interpolation based on distribution of turnover of cosmetics in Denmark and the EU:

Consumption of resorcinol in hair dye products in the EU: 90 tons
Revenue of cosmetics in EU: 54.15
Revenue of cosmetics in DK: 0.81
Danish share of EU revenue: 1.5 %

Based on the above figures, the consumption of resorcinol in hair dye products in Denmark can be calculated to 1,35 ton.

The two calculations show that the amount of resorcinol in hair dye products sold in Denmark is 1.2-1.4 tons/year. There may be significant differences between the consumption pattern for hair dye products containing resorcinol in EU countries, and the uncertainty in the calculations is assumed to be 25%. This range from 1.0-1.7 tons/year is used in the calculations of the material balance.

3.2.3.1 Fate of resorcinol in hair dye products
In permanent hair dyes, the colour component is mixed with an coupler, e.g. resorcinol, immediately prior to its use. Typically, an amount of 60 ml (with a resorcinol content of 1%) is used for colouring long hair, and half the amount is used for short hair.

Resorcinol reacts with the other substances in the hair-dyeing product very quickly. After 15 minutes, the hair is rinsed, emitting surplus colour to the waste water. Likewise, the mixing bowl is rinsed under running water.

There is no information available of the concentrations of resorcinol following the reaction phase. In the calculation on emissions to the environment it is assumed that all resorcinol will be emitted, giving a very conservative estimate.

3.2.4 Chemical industry

The Confederation of Danish Industries carried out a survey among selected companies in the chemical industry. Three companies (two glue manufacturers and one importer of chemicals) responded that they have import of resorcinol. The result of the survey is summarised in Table 3.5 below.

Table 3.5. Survey of chemical companies in Denmark

The amounts in Table 3.5 are in theory part of the imported resorcinol registered by Statistic Denmark, but it has not been possible to verify this. The figures indicate that out of the total import of 10098 kg only 2751 kg is pure resorcinol while the rest is resorcinol derivates.

3.2.4.1 Fate of resorcinol in the chemical industry
The survey performed by the Confederation of Danish Industries and the consultants did not reveal for which products resorcinol is used as a raw material or intermediate in the synthesis. It is assumed that all 2000 kg used in chemical synthesis will be converted to another chemical.

The 750 kg used for manufacturing of wood glue ends up as glue in wood products, with the same fate as described in 3.2.1.1.

The fate of the single kilo used for research in the wood glue industry is unknown.

3.2.5 Pharmaceutical industry

The Danish Association of the Pharmaceutical Industry contacted nine major pharmaceutical companies in Denmark (See Appendix 1). None of these reported any use of pure resorcinol or products containing resorcinol.

However, resorcinol is known to be used in eye drops. One product, Resorcinol Ophtha, contains 1% of resorcinol and is sold in packagings with 10 ml.

In total about 15 kg of resorcinol is used for eye drops annually in Denmark.

3.2.5.1 Fate of resorcinol in pharmaceuticals
The resorcinol applied as eye drops will enter the body in its full amount. The amount remaining when the treatment is finished must be disposed of. According to pharmacies, they receive a large amount of “old” medicine that is treated as chemical waste at Kommunekemi, most probably by incineration. Some may end up in the household waste. Also here it will be incinerated and recorcinol broken down, primarily to carbon oxides. Finally, some can expected to be emitted with waste water from households, being poured into the drain. This is assumed to be degraded at the waste water treatment plant.

3.2.6 Plastics industry

Large plastic manufacturing companies were contacted by the Danish Plastics Federation in order to obtain information regarding the use of resorcinol in plastic products (See Appendix 1). None of the companies reported production or use of pure resorcinol or products containing resorcinol.

3.2.7 Discussion of survey information

Table 3.6 below presents the information compiled by surveys in the Danish industries that reasonably can be assumed to be the main importers and consumers of resorcinol.

Table 3.6. Consumption of resorcinol (in kilos) in Danish industries in 2003, based on survey information.

The survey shows that the consumption of resorcinol in binders and hardeners is less than when statistical information from the Product Register is used for estimation. There can be several reasons for this, the most probable being that the consumption pattern has changed over the years without notifying the Product Register.

The survey also shows that there is a significant consumption of resorcinol in hair dye products. Although the consumption is estimated by extrapolation of statistical information on the EU level, the range (1000-1700 kg) is assumed to give a representative picture. Finally, the use in a certain pharmaceutical product was identified. The consumption of resorcinol in this product is assumed to be insignificant in relation to environmental exposure, but will for obvious reasons be a source of human exposure.

The survey did not reveal any information regarding export of products containing resorcinol. Based on various statistical information and assumptions, an indication of the amounts of resorcinol in wood and rubber products being im- and exported is given in the appendices.

3.3 Summary and discussion

Information has been collected from statistical sources as well as by survey of relevant Danish industries. The information is summarised in Table 3.7, the minimum amounts given in the table being best case information from the industrial survey and the maximum amounts being combined statistical and survey information using the best possible level of detail.

Table 3.7. Minimum and maximum amounts (in kilos) of resorcinol imported for processing and use in Denmark

It is noted that the maximum estimate is lower – about 5% - than the estimate based on statistical information. The difference can be ascribed to the different levels of detail of the information sources. The difference in minimum and maximum values for import of wood glue is primarily related to the content being reported in intervals, while the difference for rubber production reflects the differences between information from the industrial survey and the available statistical information. However, the range given in the table are judged to be fair estimates of minimum and maximum amounts for the flow of resorcinol in Denmark.

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Version 1.0 November 2004, © Danish Environmental Protection Agency