Cement-pozzolanic processes

Certain treatment systems fall in the category of cement-pozzolanic processes and have been in use for some time outside the U.S. In these systems, both cement and lime-siliceous materials are used in combination to give the best and most economical containment for the specific waste being treated In general, the bulk of the comments (under both classifications above) hold for techniques using a combination of treatment materials. 

Major categories of industrial waste solidiflcation/stabilization systems are cement-based processes, pozzolanic processes (not including cement), thermoplastic techniques, organic polymer techniques, surface encapsulation techniques, and self-cementing techniques (for high calcium sulfate sludges). Vitrification (discussed previously) can also be considered a solidification process. 

The HAZCON solidification process is an ex situ technology for the immobilization of metals and inorganic hazardous wastes in wet or dry soil and sludges. The technology is a cement-based process in which the contaminated material is mixed with pozzolanic materials such as Portland cement, a patented additive called Chloranan, and water. The process is capable of treating solids, sludges, semisolids, or liquids. The mixture hardens into a cohesive mass that immobilizes heavy metals. 

SOLFIX is an ex situ stabilization technology that treats heavy metals by reacting contaminated soils and sediments with cement, pozzolanic materials, and other additives to chemically immobilize contaminants into an insoluble form. SOLFIX can be used either as a stand-alone technology or it can be incorporated with Hydro-SEP (a sediment washing technology) and ORG-X (a solvent extraction technology) into a three-step remediation process termed integrated sediment decontamination system (ISDS). 

Lime/fly ash pozzolanic processes combine the properties of lime and fly ash to produce low-strength cementation. Kiln dust processes involve the addition of kiln dust to eliminate free liquids and usually form a low-strength solid. Lime-based processes for solidification use reactions of lime with water and pozzolanic (siliceous) materials, such as fly ash or dust from cement kilns, to form concrete, called a pozzolanic concrete. Wastes of desulfurization of gases and other inorganic wastes can be immobilized by this method. 

This describes the specific curing behavior of fly ash, cement dusts, and certain steel works byproducts, is based on the reaction of silicate and aluminous materials with quick lime. Here too, as with the above-mentioned additives, a higher pH causes the precipitation of metal hydroxides and carbonates. The British SEALOSAFE-Process uses fly-ash plus Portland cement, or alkali silicate glass and Fe/Al hydroxides to solidify a broad spectrum of wastes. In the POZ-O-TEC-Process, the wastes from flue gas scrubbers are solidified together with grate ash and fly-ash. The pozzolanic processes have the advantage of excellent longterm stability however, the products solidify rather slowly and are susceptible to acids. 

In hardened cement-based composites the transportation of liquids and gases through pore and microcrack systems plays a very important role in many processes, such as hydration of Portland cement, pozzolane effects of microfillers, carbonation, corrosion of cement paste and reinforcement due to reaction with external agents, shrinkage and creep, etc. These processes are partly described in respective Sections 4.1, 4.3, 6.5 and 11.5. Only basic information is reiterated below concerning the flow of liquids and gases through concretes and mortars. 

Some of the most common stabilization—soHdification processes are those using cement, lime, and pozzolanic materials. These materials are popular because they are very effective, plentiful, and relatively inexpensive. Other stabilization—soHdification technologies include thermoplastics, thermosetting reactive polymers, polymerization, and vitrification. Vitrification is discussed in the thermal treatment section of this article and the other stabdization—soHdification processes are discussed below. 

Petrifix A process for solidifying aqueous wastes, converting them to a solid form suitable for landfill. Cementitious additives are used, based on the compositions used by the Romans for making Pozzolanic cements. Developed by Pec-Engineering, Paris, France. In 1979 it had been used in France and Germany. 

Ash from pulverized coal combustion is a strategic material that has many critical applications from a source of aggregate to the most important source of pozzolan for addition to Portland cement concrete. Environmental control measures on the emissions of coal combustion have resulted in a loss of quality for these materials. In response we have seen the advent of beneficiation processes applying both proven and new technologies to produce high-quality consistent products from these materials. Currently we estimate that about one-fifth of all ash products marketed are processed through some form of beneficiation method. We expect that the demand for quality and consistency will continue and the relative amount of process ash products will increase in the future. 

Abstract Solidification/stabilization treatment processes immobilize hazardous constituents in the waste by changing these constituents into immobile (insoluble) forms, binding them in an immobile matrix, and/or binding them in a matrix which minimizes the material surface exposed to weathering and leaching. Solidification/stabilization treatment processes can include aluminum silicate and cement-based fixation, pozzolanic-based fixation, or vitrification. 

Understanding of the chemistry of autoclave processes is due primarily to the work of Kalousek and co-workers (K32,K59-K62). Above about I. SO C. for the time scales of a few hours that are used in practice, two features of cement hydration chemistry are added to those relevant at lower temperatures. Firstly, the hydration products tend to crystallize in the absence of reactive silica, C-S-H tends to be replaced by a structurally unrelated, crystalline phase, a-CjS hydrate. Secondly, the range of siliceous materials having effective pozzolanic properties is widened, and includes quartz and various other crystalline minerals, if sufficiently finely ground. 

It should be noted that lime reacts with clay particles. This leads to strength increase by pozzolanic and carbonation cementation processes. Cation exchange and pozzolanic reactions result in strength increase. The level of reactivity and hence strength gained in soil-lime mixtures depends on the level of pozzolanic product created. The chemical reaction between soil and lime can be presented as below ... 

Before concluding this subject, mention is made here of two more novel approaches for using SBE. Pollard et al. (143) have reported that SBE can be used to prepare a pseudo-graphitic char suitable as a low-cost replacement for activated carbon in the stabilization/solidification of industrial wastes. In their process, they char 2 1 blends of SBE and ZnCl2 at 450°C/1 hour and then activate the material at 600°C/1 hour. The resultant hybrid material is as effective as activated carbon for fixing toxic organics and, because of its aluminosilicate framework, exhibits additional pozzolanic activity in the cement-based stabilization/solidification reactions in which these materials are used. Very recently (144), Bohling reported on... 

Asbestos wastes may be solidified prior to their landfill burial. This may be achieved by a cementing process such as that using pozzolanic concrete, which contains fly ash or kiln dust mixed with lime, water, and additives (Peters and Peters 1980). Other processes for solidification include thermoplastic and polymeric processes. In the former, a binder such as paraffin, polyethylene, or bitumen is used. In the latter, polyester, polybutadiene, or polyvinyl chloride is used to trap the asbestos fibers or particles over a spongy polymeric matrix. The solidified waste should be disposed of in a licensed hazardous waste dump or disposal site. 

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