GEA Messo AG

Evaporation Crystallization and Chloralkali

Process Technologies by GEA Messo Switzerland

www.geamesso.com

Company Profile

Evaporation

Crystallization
GEA Messo AG is an established and international renowned firm of chemical engineering provider and process plant contractor and concentrates its business activities on a selected range of special process technologies based on a combination of extensive experience accumulated over many years in project execution, process development and cooperation with specialized companies. Since August, 2004 GEA Messo AG, has been incorporated in the GEA group, one of Europe largest technologies group. ESCHER WYSS evaporation and crystallization plants are now designed and supplied by GEA Messo AG. In 1999 the well known Chloralkali Technology of KREBS SWISS Ltd. has been taken over and the wide range of different technologies incl. complete plants for the Chloralkali industry are now designed and supplied by GEA Messo AG. With annual sales of around 4.1 billion Euros and 17,000 employees, GEA Group is an international technology based group with its core competencies in the areas of customized systems, process equipment, process engineering and plant engineering. The Process Engineering Division (P-Division) of GEA is a world leader in liquid and solid processing technologies. In total, the P-Division employs 3,300 people who produce sales of approx. 900 million Euro and provides a complete range of services and process systems to the beverage, chemical, dairy, food and pharmaceutical industries.

Salt Works

Chloralkali

Effluent Treatment

GEA Group Aktiengesellschaft

Customized Systems
I I

Process Equipment Dairy farm Systems I Process Equipment I Mechanical Seperation

I I

Process Engineering Energy Technology I Process Engineering

I I

Plant Engineering Lurgi Lurgi Lentjes I Zimmer

Air Treatment Refrigeration

GEA Process Engineering France I GEA Messo GmbH I GEA Wiegand GmbH I GEA Messo AG I Niro Inc.
I

Historical Background of Evaporation Technology ESCHER WYSS System

Evaporation plants using the ESCHER WYSS system have been built for more than 80 years. The first contract to supply a multistage compressor for mechanical vapour recompression in a salt plant dates back to the mid-twenties. ESCHER WYSS manufactured the compressors in their own workshops and were also asked to fabricate the evaporator for this plant which recovered salt from brine on a continuous basis. This project initiated ESCHER WYSSs activities in the field of evaporation technology and manufacture of the corresponding equipment. The first salt plant was followed by contracts for further salt plants as well as evaporation plants for other liquors, known frequently as concentrators. The scope of supply was limited to the main vessels, which were assembled in our own workshops exclusively until the mid-fifties. By installing a circulation pump in the centre of the calandria type evaporator the forced circulation system was created. This evaporator became famous for its excellent heat transfer rates and salt slurry handling characteristics. The drive was mounted at the top of the vapour dome and connected by a shaft to the propeller in the base. Experience grew from the widening range of applications in this special thermal separation technique. Through research and development new technologies were established and ESCHER WYSS was transformed from being a manufacturer of vessels into a contractor and supplier of technology and complete plants. The implementation of this process technology and the associated equipment was characterised by its fast progress in developing new markets, for example, in the basic chemical industry, in the treatment of wastewater from flue gas scrubbers, to name only a few. In all these plants the design was based upon achieving optimum energy utilization whilst fulfilling the environmental requirements. Evaporation plants based upon ESCHER WYSS technology were designed and supplied under the company names: 1924 - 1981 ESCHER WYSS AG 1981 - 1991 Sulzer-Escher Wyss AG 1992 - 1996 Sulzer Chemtech AG 1996 - 1999 CT Environment AG 1999 - 2000 VA TECH WABAG 2001 - 2004 Messo AG since 2004 GEA Messo AG

Technologies, Engineering and Services

GEA Messo AG supplies technology, engineering and services for: I Evaporation I Crystallization I Salt Works I Chloralkali I Effluent Treatment According to the clients requirements, we can then act as general contractor or as a partner to other firms. In connection with the supply of equipment the following services are available. Project Services I Process studies I Pilot tests I Model engineering I Feasibility analyses I Basic engineering I Quality control project management I Erection supervision I Personnel training I Commissioning After Sales Services I Technical services I Maintenance assistance I Plant management assistance Various I Studies and expertises/surveys I Pre-Engineering I R & D projects/process development I HAZOP studies I Waste heat utilization/total energy concepts I Revamping of plants

References
More than 400 plants have been implemented in all continents, many being repeat orders from satisfied clients.

Evaporation

The extensive know-how that has been gained in realizing evaporation plants gives GEA Messo AG the depth of experience needed to design new plants which are tailored to the clients exact requirements and which minimise investment and operating costs.

Multiple-effect Evaporation
Classical multiple effect evaporation uses low-pressure steam for heating of the first effect and utilizing the vapour for heating in the subsequent stage. The factor of the number of stages depends on the ratio of operating costs to capital investment which subsequently depends upon the evaporation capacity and boiling point elevation of the solution.

Characteristics of the Evaporation Processes

In the technology of evaporation GEA Messo AG is the leading designer of plants with multiple-effect and evaporation with thermocompression process and combination thereof as well as the multiple-stage flash evaporation process. We know how to engineer highly efficient processes and lay out highly efficient plants, you get lower initial investment cost and lower operating costs.
Simplified flow sheet of a six effect falling film evaporation process

Evaporation with Thermal Compression (Vapor Recompression)

We apply the thermal- or the mechanical vapor recompression. The increased fuel costs for production of steam favours the adoption of vapour compressors for evaporation plants of all kinds.

Simplified flow sheet of a MVR evaporation process

Simplified flow sheet of a multiple stage flash evaporation process

Multiple Stage Flash Evaporation

For application involving large throughputs of process solution with a relatively small rise in concentration or low evaporation ratio, the combination of multiple stage pre-heater systems for heat recovery followed by multiple stage flash evaporation is advantageous. Multiple stage flash evaporators are also economic for solutions with low boiling point elevation both from an investment and operating point of view.

Evaporator Types
To satisfy the wide spectrum of process requirements which an evaporation system has to meet, GEA Messo AG supply all evaporator types which are of proven design. Construction materials, such as: carbon steel, rubber lined, monel clad, full monel, nickel, titanium, nickel alloys, stainless steel, plastic materials etc. are utilized. GEA Messo AG design plants for the concentration of liquors mainly, evaporators with thermal recirculation and non-recurrent flow or recurrent circulation. For special cases a forced circulation system with a high heat transfer coefficient has been developed. The most suitable type has to be chosen in each case with due consideration of the main factors, namely: sensitivity of the liquor to temperature, tendency to scale, accessibility for maintenance, limited use of expensive construction materials. Flash evaporator with separate heating circuit Rising film evaporator with integrated heating chamber

References:
I National Aluminium Company Ltd, (NALCO), India, Aluminate liquor concentration, 2 lines of 135-185 tons per hour evaporation I Quimigal UNITECA, Portugal, Caustic soda concentration, 300 tons per day NaOH from 32% to 50%

Falling film evaporator

Forced circulation evaporator with integrated heating chamber

Crystallization

The extensive know-how that has been gained in realizing crystallization plants gives GEA Messo AG the depth of experience needed to design new plants which are tailored to the clients exact requirements and which minimise investment and operating costs. Super saturation is the key parameter for the crystallization and means the temporary increase of concentration of the solute in the solvent above its equilibrium, and is produced by evaporation, cooling, chemical reaction, salting out, etc. The experienced engineers of GEA Messo AG will plan, design and construct your crystallization plant for the chemical-, pharmaceuticaland food products. We know how to optimise the crystallization to achieve larger or smaller crystalls with the correct moisture content of your requirement under applying the full range of crystallization technologies.

Evaporative Crystallization
Evaporative crystallization is usually a process that is conducted under vacuum. This process is chosen when solubility of the solute is nearly independent of temperature. Special scaling problems are not a serious problem as long as boiling on the heater surface is avoided.

Simplified flow sheet of a MVR evaporation/crystallization process

Vacuum Cooling Crystallization

Vacuum cooling crystallization is usually chosen if the solubility of the substance to be crystallized is strongly dependent on temperature. Vacuum cooling crystallization is the preferred cooling crystallization method for continuous operation conditions, due to the fact that the super saturation is generated by adiabatic cooling of the solvent at the liquor level.

Crystallization Processes
GEA Messo AG has extensive experience in building plants with I Evaporative crystallization I Vacuum cooling crystallization I Recrystallization and reprecipitation
Simplified flow sheet of a multiple stage vacuum cooling crystallization process

Recrystallization
Recrystallization is applied when the feedstock is a salt/solids instead of a solvent. In the process the feed salt is dissolved in unsaturated circulation brine. Impurities are removed by decantation. The purified salt is crystallized in a vacuum cooling crystallization.

Typical examples of such processes are:

Crystallization by evaporation for the production of various inorganic and organic compounds such as but not limited to sodium chloride (salt from brines), potassium chloride, ammonium sulphate, sodium sulphate and adipic acid. Crystallizers are of continuously operated forced circulation type. They may be designed with internal or external circulation, with or without baffle zones and with no, partial or total classification.

Simplified flow sheet of a recrystallization process

Reprecipitation
Reprecipitation of salt is carried out by dissolving of a salt in the mother liquor and simultaneously precipitation of the product salt. This process is applied in cases of different solubility behaviour of the two salts.

Crystallizer types
The control of super saturation, crystal suspension density and crystal breakage requires forced circulation evaporation systems. GEA Messo AG design the crystallizier for all sizes, materials of construction, with integral heating chambers, with external heating circuits or with combiened circulation systems for special quality of crystalls.

References:
I Bitterfeld, Germany, salt/sulfate crystallization, 10.9 tons per hour salt plus 0.29 tons per hour sulfate I SOM Nitratos, Chile, potassium nitrate crystallization, 12.5 tons per hour

Salt Works

GEA Messo AG can supply the complete plant to process whatever type of salt resource you have solar salt, rock salt, sea salt, or brine from solution mining into whatever type of salt you need: moist or dry, fine or course, cubic, spherical or dendrite, white, free-flowing, with additives (e.g. potassium iodide), packed in bags, bottles, or boxes, salt for the table, factory, farm, or icy road. Depending on the raw material and plant design, we can achieve purity up to 99.99% NaCl. The utilization of natural salt resources depends upon the geological characteristics, the requirements of the end-users and economical aspects. These considerations are decisive in the selection of the most suitable technology to satisfy the quality requirements for vacuum salt. GEA Messo AG has supplied more than 100 plants and is world leader for mechanical vapour recompression technology and combined sodium chloride/sodium sulphate plants. The extensive know how that has been gained in realizing these plants gives GEA Messo AG the depth of experience needed to design new salt plants which are tailored to the clients exact requirements and which minimise investment and operating costs. GEA Messo AG is re-known worldwide for the design and supply of vacuum salt plants which match the individual requirements of table salt as well as for producing high grade vacuum salt, suitable for Chloralkali electrolysis plants.

Simplified flow sheet of combined NaCI/Na2SO4 process

We choose the most efficient and economical technologies for each plant:
I I I I I Chemical brine purification Multiple-effect evaporation crystallization Mechanical vapour recompression Thermal vapour recompression Recrystallization

and we build all types of plants:

I Common salt production plants I Brine purification plants I Vacuum salt plants using purified brine for super high-grade salt I Complete vacuum salt plants with brine purification, storage, bagging, logistics I Recrystallizer plants for the production of vacuum salt I Combined plants for high purity requirement The most common crystallizer type used for salt is the Forced Circulation Crystallizer (FC-type). GEA Messo AG has extensive know how and experience in designing the components in special material of construction like monel, titanium, special alloys and stainless steel.

References:
I Pimai Salt Company, Thailand, 5 table salt plants, production rate: 15, 30, 45, 60, 60 tons per hour salt I Jintan Saltworks, China, table salt plant, production rate 87 tons per hour

Chloralkali

GEA Messo AG offers the complete range of process technologies for the production of Chlorine, Caustic Soda, Sodium Hypochlorite, Hydrochloric Acid and Iron (III) chloride. The basis is a combination of extensive experience, close cooperation with leading membrane cell electrolysers suppliers, process development in own laboratory and cooperation with specialized companies and with scientific institutions.

The experienced engineers of GEA Messo AG will plan, design and build your Chloralkali plant or process unit for the production and treatment of chlorine, caustic soda/potassium hydroxide and hydrogen by electrolysis of NaCl or KCl brine and related plants including: I Chloralkali electrolysis plants in collaboration with leading electrolyser providers, I Chlorine processing and handling plants I Nitrogentrichloride removal and decomposition units I Brine preparation and purification plants I Hydrogen processing plants I Chlorine absorption and sodium hypochlorite production plants I Processing and concentration plants for caustic soda or potassium hydroxide I Iron (III) chloride production plant

GEA Messo AG provides all services required for the execution of complete Chloralkali plants or of specific designed process units. We are available to our clients as required by the specific project.

10

Chloralkali electrolysis
GEA Messo AG is cooperating closely with leading membrane cell technology providers and will safeguard the implentation of the electrolyser technology in the Chloralkali plant. The related process section for feeding of ultra pure brine to the electrolysers and for the processing of the products generated in the electrolysers will be designed and supplied by GEA Messo AG for the specific requirements of the electrolysis technology.

Chlorine processing and handling

GEA Messo AG design and supply chlorine processing and handling facilities to match exactly the clients requirement and can includes some or all of the following process steps: I Cooling and filtration I Drying to achive lowest possible moisture contents I Scrubbing to remove Nitrogentrichloride and/or Bromine I Safe decomposition of Nitrogentrichloride I Compression with liquid ring-, reciprocating pistonor centrifugal compressor I Liquefaction to achieve either highest efficiency or highest liquid chlorine quality. I Storage and transfer of liquid chlorine I Filling into containers/ tonners and bottles I Evaporation. I Normal vent gas and emergency absorption into caustic soda.

Brine preparation and purification

Most of Chloralkali electrolysis plants build by GEA Messo AG are operated with brine prepared from local salt, the companys experts are consequently familiar with the particularities of the salts available in many different countries. They can thus optimize the concept for any particular brine preparation and purification plant. The teams vast experience will give optimum results independent of whether the feed stock is vacuum salt, solar sea salt or rock salt. Our specialists will evaluate the most economical alternatives for some or all of the following process steps: I Primary brine dechlorination I Secondary dechlorination I Saturation I Chemical treatment I Clarification I Filtration I Ion exchange purification

Iron (III) chloride production

Iron (III) chloride is a very popular agent for the treatment of both drinking water and waste water, where it is used as a flocculants. The process using chlorine gas and scrap iron has been continuously perfectioned and the emission from the plants are negligible whereas the product quality is outstanding.

References
I Borregaard, Norway, Chloralkali plant for 140 tpd NaOH with bipolar membrane electrolysers of AGC, conversion project. I THASCO, Thailand, Chlorine drying units for up to 200 tpd chlorine gas containing < 15 ppm moisture.

11

Effluent Treatment

GEA Messo AG specializes in treatment systems for process streams and wastewater containing inorganic and organic chemicals. We apply our evaporation and crystallization technology to efficiently treat: I I I I I I Effluents from flue gas scrubber Process liquor from TiO2 plants Waste acid from scrubber Waste liquor from pulp- and paper plants Waste water from incineration plants Process waste streams from industrial plants

GEA Messo AG applies the following evaporation and crystallization technologies:

I Multiple effects I Thermal and mechanical vapour recompression I Evaporative crystallization I Vacuum cooling crystallization The most common evaporator and crystallizer types used are: flash, rising film, falling film and forced circulation evaporator as well as the forced circulation type crystallizer. GEA Messo AG has extensive know how and experience in designing the components in special material of construction like carbon steel, rubber lined, special alloys, graphite, plastic materials such as FRP, FEP and silicon cast iron etc.

In various industries ranging from titanium dioxide, magnesium oxide, pulp and paper to chemical processing, GEA Messo AG implemented complete effluent treatment solutions. The systems are built to recover I I I I I I I Ammonium sulfate Sodium sulphate Sodium chloride Sulfuric acid Calcium chloride Inorganic mixed salts Hydrochloric acid

12

Examples: Treatment of Waste Sulfuric Acid

The treatment of waste acid from the production of TiO2 is illustrated as follows. The production of white pigment by the older of the processes in use today is based upon the leaching of ilmenite ore with H2SO4. For every ton of TiO2 product, about 8 tons of waste or weak acid with approximately 20% sulfuric acid is produced. This stream which is contaminated with many soluble impurities is treated in a two stage process. The treated acid can be reutilized for ore leaching. Through systematic recycling, pollution of the oceans can be avoided.

Waste Water From Flue Gas Cleaning

Design and supply of plant for recovery of salt, calcium chloride and gypsum from flue gas scrubber. The plant is specially designed to crystallize and separate the salts.

References:
I Borsodchem, Hungary, Treatment of waste water to recover sodium chloride, capacity 4.25 tons per hour NaCl I Nordenham, Germany, Treatment of waste sulfuric acid

13

Quality Assurance

The core of the ISO 9000 Quality Standard is a series of five international standards that guide the development and implementation of our effective quality management system. Placement companys ISO 9001 : 2000 certification demonstrates our commitment to ensuring a consistent, world-class level of quality throughout all our business processes and management in our quest to develop,

design, fabricate, implemented processes, equipment and plants at exceptional customer service. The management system of GEA Messo AG is implemented since 1993, approved and certificated by the Bureau Veritas Quality International.

14

15

GEA Process Engineering France Kestner Division

4, Rue Jean-Pierre Timbaud, BP 80, Montigny le Bretonneux F-78185 Saint Quentin en Yvelines Cedex Phone: +33 1 30 14 61 10 Fax: +33 1 30 07 18 19 www.gea-pe.fr

GEA Messo AG is part of the Process Engineering Division of GEA Group and of the Strategic Business Unit Evaporation and Crystallization consisting of the main companies: I GEA Process Engineering S.A.S (Kestner Division), France I GEA Messo GmbH, Germany I GEA Wiegand GmbH, Germany I Niro Inc. (Evaporation and Crystallization Division), USA I GEA Messo AG, Switzerland The range of activities of GEA Messo AG covers: I Salt plant technology and supply of complete vacuum salt plants I Plants for concentration of effluents (process waste streams) and/or recovery of valuable by-products I Plants for concentration and disposal of flue gas scrubber effluents containing hydrochloric acid, various salts and impurities I Concentration and crystallization units and plants for the chemical, metallurgical and fertilizer industry (process streams) I Plants utilizing various process technologies for Chloralkali industry

GEA Messo GmbH

Friedrich-Ebert-Strae 134 D-47229 Duisburg Phone: +49 20 65 90 30 Fax: +49 20 65 90 32 99 www.messo.com

GEA Wiegand GmbH

Einsteinstrae 9-15 D-76275 Ettlingen Phone: +49 72 43 70 50 Fax: +49 72 43 70 53 30 www.gea-wiegand.de

Niro Inc.
9165 Rumsey Road US-21045 Columbia, Maryland Phone: +1 41 09 97 87 00 Fax: +1 41 09 97 50 21 www.niroinc.com

GEA Messo AG
GEA Messo AG, Brglistrasse 29, CH-8400 Winterthur, Switzerland Telefon +41 52 234 00 00, Telefax +41 52 234 00 99, Email: contact@geamesso.com, www.geamesso.com