Patent Application
20100137126
The invention concerns a mixed product of organic and inorganic particulate materials and/or material mixtures with an auxiliary material used (or auxiliary mixture) therein. The auxiliary material (or auxiliary mixture) is an additive which lends different properties to a final product. The properties of the product are calculable and adjustable thereby before commencement of manufacture. Depending upon starting material and the desired properties of the final product the auxiliary material is added. The auxiliary material leads to the formation of crystal structures and fulfils (depending upon the final product) different functions:
Certain mixed products can be used as energy stores, whereby the energy store quantity is adjustable. Further other ones of the mixed products can be used as reducing agents in different applications. Depending upon the mixed product, a use can, for example, be for the treatment of drinking water, for metal finishing or during wood processing and paper processing. All of the end products manufactured from the mixed product can be optimised with respect to target properties. For example, paper and cardboard that have been treated with this mixed product exhibit hitherto unknown stability and stiffness. The improved paper or the improved cardboard is similar to a reinforced plastic tube in one aspect of the present invention with respect to these properties.
Such mixed products are known e.g. from WO 1996/06060 A. This document describes a palletized product manufactured from sludge and a silica-like, pourable bonding agent with fine minerals, aerated concrete or saw mill residue by applying several compression steps, with intermediate decompression. The palletized product can be used in agriculture or placed in rubbish tips safely.
From DE 101 60 163 A, a product is known for use in a cement clinker rotating furnace to make a product from sludge and fly ashes and thus save lime.
It is known from DE 198 48 432 A to transform a product of sewage sludge and sewage sludge residuals or tar oil or similar products by pressing into a state which permits the thermal use of the product for fixed bed high-pressure gasification.
An object of the invention relates to the creation of a material composed of an organic and inorganic particulate material and/or material mixtures with a high specific internal surface; i.e. a high adsorptive capacity for as many polluting materials as possible, for example oil, exhaust gases and harmful particles, for e.g. exhaust particles and physicochemical properties for the immobilization of environmentally harmful materials, for example toxic materials. The desired materials should be easily manufactured from economical raw materials in a conventional way.
This problem is solved according to the invention by organic and inorganic particulate materials and/or material mixtures forming together a substantially homogeneous matrix. 75 to 85 weight %, preferably around 82 weight % of the dry weight of the starting material is a residue. The residue is substantially free from metallic material. The problem is further solved in that the residues are additives of 80 to 90 weight % with respect to the dry total quantity of additives. The additives are made of clay, inclusive of bentonite, zeolite and lime, whereby the remainder is lignin and/or lignin derivatives. The particle size of the material and/or material mixtures forming the substantially homogeneous matrix is between 50 μm and 3 mm.
A “homogeneous matrix” in the description and the claims is to be understood as a structure that when microscopically seen provides the mixed product in different places with the same properties. The carrier materials and the embedded materials therein are still distinguishable when microscopically seen. These properties result from the crystal structure created by means of the mixture.
The invention is based on the recognition that mixed products having kalzit (CaCO3), rutile (TiO2) and ankerit (CaMgO.77FeO.23(CO3)2) of small size in the weight ratio (70% to 95%):(2 to 15):(2 to 15), allow the formation of a matrix with the desired properties. It is not necessary that these three components are present to a large extent within the mixed product. Rather to the contrary, it is sufficient that they provide 3% to 5%. If necessary in individual cases 8 to 10 weight % of the listed additives are present. Rutile and ankerit do not have to be evenly distributed.
The associated relative mass ratios of the components of the additive materials are: oxygen 50-55 magnesium 1.0-1.5, calcium 32-38, titanium 1-2 and iron 0.7-1.5. This is achieved by taking into account the composition and the quantity of the other materials, including those elements which do not promote the formation of the matrix materials.
These values do not require exact observance as compared to chemical reactions, having firm stoichiometry, since a surplus of components can stay simply as a kind of “filler” or can escape accordingly from the matrix. The filler deposits itself in the matrix, which otherwise would be a homogeneous matrix.
The invention is described in more detail, by means of the following figures:
The following exemplary description of a method for the manufacture of a mixed product according to invention is explained with reference to
The raw materials to be processed are analyzed before the introduction into the manufacture, by a method specified below. Data is received from this analysis. The received data of this analysis are input into a process computer. The process computer uses the received data for the creation of a suitable recipe. This recipe can be easily determined from the measured composition of the raw materials taking the above points into account. Of course it is possible to carry out this determination using a computer program, as the determination substantially corresponds to the solution of a system of linear equations.
The input values for the starting materials, e.g. sludge, paper sludge, plastic materials, wood, composites, made of plastic and wood, products of the mechanical-biological residual treatment, bone meal, oil remainders, hydrocarbon and hydrocarbon residual substance products, e.g. roofing felt, tar covers and/or organic residual substance products, as gravel-wash dredges e.g. sediment materials, reservoir sediments, side materials or power station fly ash, are different. In a preparatory step, it is ensured that the maximum particle size of the single components is 300 mm is achieved by means of a shredder 1. The cut up parts of the starting materials are conveyed substantially by means of conveyor 2 to a first processor (K1) 3, whereby metals are separated by separators. A separation of the metals also takes place within the first processor (K1) by means of centrifugal force. The weight of the conveyed material is measured automatically with a belt weigher ‘(not shown). The received data are then also entered into the process computer. In the first processor (K1) 3 the starting materials are further reduced in size to a size of smaller than or equal to 3 mm This repeated reduction in size takes place, for example, via rotation apparatus (not shown) which can have a high rotation speed of up to 2800 U/Min over a length of up to 1300 mm A further separation takes place later within the second processor (K2) by means of centrifugal force and additionally by means of a metal separator. During this repeated size reduction process a large amount of energy is added to the starting materials which leads to an evaporation of the water content. Up to 90% of the water content evaporates. The arrangement of the rotation apparatus is aligned in such a way, such that up to 90% of the starting materials have a size that does not exceed 1 mm
After treatment of the starting materials in the first processor (K1) 3, the prepared raw material is analyzed. Different measurements are carried out. In particular the following data is measured:
The measured data is measured by means of measuring points along the conveyor and input into the process computer and compared with the values of the recipes given below. This analysis leads to the sending of appropriate control instructions to the mixing and dosing program which is upstream of a second processor (K2) 7. In the second processor (K2) 7, the second process stage takes place. The input of the materials corresponding to the recipes takes place in the dosage unit of the second processor (K2) 7.
A counting wheel lock or a similar technical device is arranged as the dosage unit. The dosage is based on the recipe which is automatically selected by the computer mentioned above.
In the second processor (K2) 7 the individual components of a first material mixture are multiply reduced to a size smaller than or equal to 50 μm. The portion of materials having a fine grain of 3 mm, i e a diameter over 3 mm is about 5%, and the proportion of materials with a 1 mm fine grain is about 8%. The remainder is fine grain with a diameter of under 1 mm The main component has a size of less than 100 μm. This fine particle size distribution relationship is relevant for the stabilization of the mixture.
The first material mixture is passed to the conveyor 17 after the treatment in the second processor (K2) 7.
The same measurements as described above take place. Further remaining metals from the first material mixture are separated such that no metal is further found to a degree of 99%.
The input of the material mixture 21 into the third processor (G1) is followed. This is done by means of the conveyor 17. As can be seen the first material mixture can be conveyed by a further dosage unit.
A first intensive mixing takes place in the third processor (G1) 21. Further additives are added to the first material mixture according to the recipe. The portion of the first material mixture amounts to about 85%. Thus about 15% of additives are added. The first material mixture is brought back on to a conveyor 25 (or similar conveyer system).
A check measurement takes place by means of inserted sensors in the area of the conveyor 25. The same measurements are carried out as described above. The mixed product is then forwarded by conveyor 25 to a fourth processor (G2) 34. A subsequent adjustment of the composition takes place via the addition of further additives. Usually a second material mixture is created which consists of 0 to 5% of the newly added additive and to 95 to 100% of the first material mixture. The transport takes place by means of a fourth dosage unit at the fourth processor (G2) 34.
The second material mixture is brought again on to a conveyor and passed for treatment. The passage to treatment can take place via a pellet-making device and a drum filter. The mixed product is created according to the invention.
Subsequently a pre-defined quality control takes place. The same measurements as made above are carried out and furthermore the pellets are sorted. Once the quality standard of at least 99% is reached the product is passed to the storage 38.
If the predefined quality standard is not reached, i.e. if less than 99% of the product corresponds to the desired composition, the second material mixture is passed to a “reject chute”. From there the rejected second mixture is supplied to the process again in a proportion of less than 10% “reject material” to more than 90% new materials. The new mixture is subsequently regarded as starting material when it comes to the calculation of the additives. A reason for the non fulfilment of the predefined quality control standard is that the mixing ratio of 75 to 85% of organic components and thus 25 to 15% of inorganic components in the starting material and/or starting materials is not present. If this mixing ratio of the starting materials is not present, the desired crystal structure can not be sufficiently formed.
An advantage of the mixed product according to the invention resides in that cheap secondary raw materials can be used for its manufacture. The mixed product according to the invention is a starting product for further end products. The end product has residual materials as its starting point, so that in a use an ecological balance is attainable.
In addition it is desired to use inorganic bonding agents predominantly manufactured from residual materials as inorganic materials. Thus the undesirable use is avoided of conventional inorganic materials like inorganic bonding agents made using a lot of energy and from relatively expensive raw materials and may cause substantial damage to the natural landscape.
Further aspects of the invention are to be found in the dependent claims and the following description.
It should be noted that the recipe of the mixed product is adapted to the desired end products. This recipe governs the choice of the appropriate residual substances and/or residual substance mixtures and also the additives which are added for the formation of the mixed product. Thus the material properties of the mixed product having a material specification are tuneable. Likewise by adding additives, the properties of the mixed products in each of its various forms are tuneable according to use.
The mixed product according to invention is according to its composition the starting material for further subsequent products and subsequent applications. The mixed product can also be in addition itself a final product. The mixed product can be used, for example, as exhaust and particle filters to remove CO2 at low temperatures and also further pollutants from exhaust gases, for example industrial pollution gases. Certain pollutants can be removed even at higher temperatures. However this application is only beneficial to the ecological balance if the further processing of the loaded material does not lead to a repeated release of the CO2. A drying process of the mixed product occurs at the same time with the employment as a CO2 filter in the low temperature range, as well as a reduction of the pH value.
The mixed product is suitable also as an aggregate in the building materials industry e.g. as a filler for concrete products in ditch, channel and road construction, as well as a filler for noise control and embankment construction elements.
Further a use is possible in the metal processing, wood treatment and paper treatment industries.
The treated mixed product is also used for drinking water processing. A reduction of the bacteriological content and heavy metal content can be obtained by using iron compounds.
A further use of the mixed product is as an effective reduction compound and immobilization means for chrome VI containing wastes. A reduction of chrome VI takes place to chrome III. Chrome VI is regarded as one hundred to one thousand fold more toxic than chrome III and is much more mobile than chrome III.
For this application the mixed product is conditioned with ground clay and a small quantity of H2SO4 (pH value approx. 3) as additives. This mixed product is an effective reducing agent for chrome VI. After the reduction of chrome VI to chrome III in a weakly acidic environment, buffering to a neutral value and heavy metal stabilization is achieved by addition of ground limestone (with a grain size less than 200 μm).
The mixed product in baked form is a ceramic material with large specific surface which is usable together with the starting mixed product for the production of an oil binder. An oil binder e.g. for use in water is prepared from a combination of the starting mixed product and from mixed products that have certain components baked at low temperatures and certain components baked at high temperatures. The oil binder is dried in air, ground and/or pelleted.
The mixed product is also used in the tyre industry and leads to the reduction of the rubber-specific lubrication behaviour so that a reduction in a braking distance and a higher life span is achieved. The mixed product is used in animal husbandry as animal litter, agriculture, horticulture and landscape gardening for the improvement of the soil properties with respect to water retention and fertilization.
The following materials can be used as residual substances in the mixed product of the invention: sludge, paper pulp sludge, plastic materials, wood, composite materials from plastic and wood, products of mechanical-biological waste treatment, bone meal, oil remainders, hydrocarbon and hydrocarbon waste derivative products, e.g. roofing felt, tar covers, residual substances with substantial organic and/or inorganic residual substances, such as gravel-wash dredge e.g. sediment materials, reservoir sediments, or side materials, power station fly ash or other ashes.
A treatment of “pasty” residual substances (e.g. oil mud) takes place in each case according to the logistical situation. The treatment is either directly for the production of a processable organic rich components for later mixture with mineral additives or is the treatment with a selection of mineral additives and the baked mixed product followed by grinding to a grain size of less than 200 μm. The subsequently in a mixed formed pumpable substance is led into an activator via a sieve feeder. A homogenising and mechanical disaggregation is achieved by adding additives such as quicklime, clay flour and starting mixed product
The prepared residual substances are added with residual substances not requiring further treatment. Subsequently a measured addition of these added residual substance components with mineral additives takes place using a mixture of mineral additives. The mixture of mineral additives is adapted to the product chain and the product application. A required organic-mineral additive (ground clay with lignin derivatives) is added.
The most important components of the mineral additives and/or additive mixture of the mixed product are:
Important tasks of the organic rich residual components, including liquid, “pasty” and solid hydrocarbon residual substance products in the mixed product are:
Main tasks of the mineral additives in the mixed product are:
Manufacturing process for the mixed product as a function of residuals and the use-specific additives including pre-treatment of residual substances and inorganic additives
The recipes for the mixed product are selected as a function of the intended use and/or on the intended subsequent product:
Manufacturing process of mixed product “baked” from mixed product “dry” for the manufacture of oil binders for the use on land
Manufacturing process of baked, broken mixed product from the starting mixed product, mixed product “dry” and/or mixed product “baked” as well as recipes for the manufacture of oil binders for use on water:
To aid in the understanding of the mixed product according to the invention and the method for manufacturing of the mixed product some powder diffractograms are attacked. A sample before the treatment and a sample after treatment were analyzed in each case in order to demonstrate the chemical conversions as described above. The results of measurement of the powder diffractrometry are attached as diagrams.
The following starting materials result in the case of the mixed product according to invention:
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2007 006 137.6 | Feb 2007 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP08/00960 | 2/7/2008 | WO | 00 | 1/21/2010 |
