NL1005470C2 - General construction material production from waste materials - Google Patents

Abstract

Waste material, e.g. fly ash, asphalt and similar, is treated by mixing with binders in a pre-determined ratio. A matrix is produced by allowing one or more binders to react with the material under pre-determined reaction conditions, so that contaminants present in the waste material are immobilised and not removed by leaching. Also claimed is a construction material, e.g. a sand replacement, obtained using the method described above. Also claimed is the production system for the material consisting of a mixer and a reactor, preferably an autoclave.

Description

METHOD FOR PROCESSING WASTES, SUCH AS FLYGAS, AND A BUILDING D material obtained by means of this method

The present invention relates to a method for processing waste material, a building material comprising such processed waste material and a system of equipment for carrying out such a method.

Disposal of waste materials, such as fly ash from waste incineration plants (incinerator fly ash) and power plants (e-fly ash), and asphalt filter dust is an increasing environmental problem due to the environmentally hazardous substances contained in this type of waste material, and is also an economic problem.

An object of the present invention is to provide an improved method for processing waste material.

The present invention provides a method for processing waste materials such as fly ash from a waste incineration plant, a power plant, asphalt material, in particular asphalt filter dust and the like, comprising the step of mixing the waste material with one or more predetermined binders in a predetermined ratio , followed by subjecting the resulting mixture to a matrix-forming step, whereby under predetermined reaction conditions, the one or more binders and the waste material react together to form a matrix, in which matrix substantially contaminants contained in the waste material are immobilized in such a way as to prevent leaching of these impurities from the mixture.

10054 7 ü 2

When processing the waste material, the environmentally hazardous substances contained therein are substantially immobilized. Immobilization means: a technological intervention in which the physical and / or chemical properties of a waste material are changed in such a way that the spread of environmentally hazardous substances through leaching, erosion or spraying is reduced in the long term.

The inventors have shown that a mixture obtained by this method shows a very low value for leaching of environmentally hazardous substances.

In order to give good results and to facilitate the treatment of the waste materials, the method may comprise one or more of the following steps: - subjecting the mixture of waste material and binders obtained by the above step to a homogenization step; and - compressing this mixture, preferably in the form of briquettes, to compress the composition into a solid element before subjecting the mixture to the matrix-forming step.

These briquettes can then be broken and further preferably subjected to one or more washing steps in order to wash out highly leachable parts, such as salts, for example chlorine and bromide.

Further preferred features of the method of the present invention can be found in claims 6-13.

According to another aspect of the present invention, there is provided a material obtainable by the above method.

The inventors have found that a material obtainable by this method, such as building material, for example as a substitute for sand, can be used, which building material mainly complies with the leaching standard according to the leaching characteristics of solid earthy and stony building materials and waste materials. 3 in accordance with the Building Materials Decree on soil and surface water protection. This Decree is a General Administrative Order, the legal framework of which is formed by the Surface Water Pollution Act and 5 Soil Protection Act. The decision has been published in the Dutch Official Gazette No. 567 of November 30, 1995. It will enter into force on January 1, 1998. The leaching is tested via the column test in accordance with NEN 7343. In this way, an effective building material can be provided, which also includes 10 environmentally hazardous waste materials. cleared away.

According to still another aspect of the present invention, there is provided a system of equipment for performing the above method to provide the above material.

The invention will now be further elucidated with reference to the following specific description and examples, referring to the accompanying figure, which shows the conditions under which the matrix-forming step for one of the mixtures was performed.

All leaching results indicated in the tables were obtained by means of the column test described in NEN standard 7343.

Fly ash from the waste incineration plants in Alkmaar, Roteb and Avira, fly ash from various power plants, and asphalt filter dust from customers of Winterwijksche Steen-Kalkgroeve (producer of filler for asphalt, among others) have been used as raw materials.

30 samples of these raw materials were examined for composition and leaching. These samples were subjected to the column test in accordance with the requirements of NEN 7434.

The results of this are shown in Table 1 below.

1005470 4

Table 1

Composition and Leaching Starting materials __Monileroodj__ —_____ d AVl-vieq »»

Degree of pi I

GeMtfbaathcid Ec

DroopyU Im / m% l _________ 5__ | m / m% | InVm% | | m / m% | AVI vtiegas mat. 100 kWv »ega« unground E-v9tgi »100

Sand Poop

OngaUuate Poop

AalaMHent to 100

Vomuand _Roel_______ _

Composition Leaching L / S * 10 Composition ÜHioglng L / S «10 Composition UHIoglng L / S« 10 ___ Img / kg dal_ | mn / kgd »| | mg / kg d »| _ [mg / fcg ds | (mg / Kg ds] _Irog / kq dsl

Arsenic As 100.00 0.06 45.00 0.03 5.50

Barium Ba 370.00 0.61 560.00 1.90 660.00

Cadmium Cd 340.00 0.05 12.00 0.01 1.Θ0

Chrome Cr 130.00 0.01 34.00 0.31 22.00

Coball Co 15.00 0.05 10.00 0.05 4.60

Copper Cu 830.00 0.10 96.00 0.10 22.00

Mercury Hg 1.70 0.00 0.40 0.00 = 0.10

Lead Pb 6 000.00 1.43 250.00 0.10 65.00

Molybdenum Mo 23.00 7.97 16.00 8.90 '10.00

Nickel NI 44.00 0.10 26.00 0.10 14.00 η r Antimony Sb 130.00 0.15 34.00 0.25 c 2.00 * 3 Selenium Se 15.00 0.03 22.00 0.40 '2.00

Tin Sn 1 100.00 0.05 43.00 0.05 7.20

Vanadium V 29.00 0.05 120.00 1.70 20.00

Zinc Zn 24 000.00 0.76 600.00 0.10 260.00

Fluoride tolal F 16.00 10.18 25.00 11.00 4.40

Cyanide free CNvrlj 5.00 0.05 5.00 0.05 "5.00

Cyanide complex CN com 5.00 0.05 5.00 c 5.00

Sulphate S04 19 000.00 28 613.23 9 000.00 12 000.00 1 200.00

Bromide Br 1 000.00 920.10 49.00 39.00 2.00

Chloride Cl B7 000.00 66 595.31 850.00 3 000.00 650.00 O Strontium Sr 240.00 260.00 110.00 Δh Tungsten W 380.00 19.00 5.00 EOX 5.5 <0.10 0.94

Mineral Oil 500 <10.00 1 000.00 PAH Tolaal 16 75 (10) '0.50 6.20 _ && 2ÊQ_LjiS_fe_0 05 0-05

From these raw materials, 5 different base compositions, k9605WO1, k9605WO2, k9605WO3, k9605WO4 and k9605WO5, each of 5 tons, were composed and homogenized.

Subsequently, the composition 9605W04 was mixed in a mixer, Turbomix 10.07 from the company R.T.eL. from 30 Eibergen, brought in to react the quicklime with water. About 500 kg of water was added to a 5-ton mixture at a temperature of 95 ° C. This mixture contains quicklime. Quicklime must react with water before it is processed in the briquetting press. This is because the lime expands in this reaction, causing the briquettes to crack. The water added in the Turbomix 10.07 had a temperature of 95 ° C. This high temperature is necessary to start the reaction between the quicklime and the water. After this reaction, the moisture content in this mixture is 0%. Namely, as much water is added as is necessary to quench the lime and what will evaporate through the heat. The residence time in the Turbo mix 10.07 was ± 24 hours.

Subsequently, the compositions were converted into briquettes in a briquetting machine of the type Brikett-Mobil Köppern 115 KW under a variable pressure of between 15 kN / cm and 60 10 km / cm.

Prior to this step, water needed as a binder in the briquette machine was added. The water was mixed into the compositions in a flow-through mixer, the residence time in the mixer was ± 2 minutes.

The compositions were then autoclaved in the matrix forming step.

L at the end of the code means that the composition was autoclaved on a small scale in a test set-up in 20 Amerongen (NL) at 16 atmospheres.

D at the end of the code means that the mixture was autoclaved in Germany by the donation at Halten in an autoclave.

Figure 1 shows the conditions in the autoclave of 10 tons of curing 9605WO1 to 9605WO5, each of 2 tons, when autoclaving.

After briquetting and autoclaving the different compositions, they were determined in accordance with the Dutch standard NEN 7343 for their leaching characteristics with the column test.

In this column test, the material is placed in a column and then flowed through with a fixed amount of water. This water is analyzed, from which it follows that in which amount a certain component leaches (mg / kg).

1005470 6

Results of this for the different compositions are shown in Tables 2 and 3 below.

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These tables 2 and 3 indicate, among other things, the different weight percentages of the amount of raw material and binder per composition.

These compositions were analyzed. The 5 results of these analyzes are also shown in Tables 2-4.

Table 4 Civil engineering parameters 10

Density Mas- Water absorption Water absorption Crushing sa (density) [% m / m] Vacuum factor [kg / m3] [% V / V] [-] W01 D 1770 19.9 29.4 0.74 W02 D 1730 21, 4 30.6 0.71 W03 D 1600 25.5 34.1 0.72 15 W04 D 1850 17.4 26.0 0.76 W05 D 1470 32.0 35.5 0.62 W02 4.8 D 1730 21, 1 23.1 W02 6 D 1760 19.5 22.7 AVI bottom ash 1900 ± 20 0.67 20 Concrete granulate ± 1830 ± 15 0.75-0.84

The briquettes were then broken to yield a granular material with an average grain size of about 20 mm or less.

Briquettes of the composition No. 9605WO2 were broken and the resulting granular material was analyzed according to the column test before leaching.

Furthermore, composition 9605WO2 was washed, under conditions of about 20 ° C for 1 day 1005470 with a liquid / solid ratio of 4 (4 times as much water as solid), to give highly leachable components such as salts, for example Cl ', Br ", wherein the leaching rate was also analyzed after washing.

The results are shown in Table 5.

10054 7 n 11

Table 5

Mixture Number 9605W02_ f 1 1 For Washing Post-washing »Sample code I I K9605W02L '9605W02 j

Ratio corrected. L / S cor. Cor. with regard to dry matter 10.00 10.00

Ratio US 10.13 i 11.11 c Acidity pH 12.00 11.80

Conductivity pS / cm 11000 9500

Dry residue _% _ 0.99_j_OjgO_ _! _ I _; _ j

Standard category N2 E (US = 10) Test E (L / S * 10) Test _l_ (mo / koi_1 tma / ko d.s.l_N2 'fmo / ko d.a.l_N2

Arsenic As 1 7,000 <0.025 OK

Barium Ba I 58,000 0.450 OK!

Cadmium Cd 0.066 <0.010 OKI

Chrome Cr 12,000 0.083 OK: 10! Cobalt Co 2,500 y <0.050 OK.

I Copper Cu 3,500 | «0,100 OK

Mercury Hg! 0.076 i «0.001 OK:

Lead Pb! 8,700 | 0.720 OK '0.600 OK

Molybdenum Mo 0.910 | 0.550 OK 0.400 OK

Nickel Ni 3,700 l <0,100 OK

Antimony Sb 0.430 j <0.025 OK j

Selenium Se 0.100 y <0.025 OK 0.025 OK:

Tin Sn 2,400 «0.050 OK j

Vanadium V i 32,000 j «0.050 OK l

15 Zinc Zn 15,000! 1,200 OK

I 1! j

Fluoride total F j 100,000 6,000 OK \

Cyanide free CN free 0.076; 0.060 OK

Cyanide complex CN com! 0.380 y 0.060 OK

Sulphate S04 | 22,000,000 I 10,000,000 OK 7,500,000 OK!

Bromide Br 4,100 y 260,000 Exceedance 1,300 OK! '

Chloride_Cl! 8,800,000 I 24,000,000 Exceed 1,200,000 OKÏ

Standard category NI E (L / S = 10) Test E (L / S = 10) Test

_ΐ_ [mg / kg] _l [mg / kg d.s.] _ N1 [mg / kg d.s.] _ NV

2 o Arsenic As: 0.880 i «0.025 OK

! Barium Ba 5,500 | 0.450 OK!

Cadmium Cd j 0.032 i <0.010 OK j

Chrome Cr 1,300! 0.083 OK

Cobalt Co 0.420 · 0.050 OK

Copper Cu 0.720 i <0.100 OK j

Mercury Hg j 0.018; <0.001 OK ji

Lead Pb! 1,900: 0.720 OK '0.600 OKyy

Molybdenum Mo I 0.280 j 0.550 Overrun 0.400 Overrun; j Nickel Ni j 1,100 [<0,100 OK!, 2 5 I Antimony Sb I 0,045! <0,025 OK '

Selenium Se; 0.044! «0.025 OK 0.025 OK

Tin Sn 1 0.270; <0.050 OK)

Vanadium V j 1,600 ': <0.050 OK l,

Zinc Zn i 3,800 1,200 OK «

Ruoride total F (13,000 y 6,000 OK

Cyanide free CN free 0.013 | 0.060 Exceedance ï

Cyanide complex CN com: 0.067 y 0.060 OK. j:

Sulphate S04 i 750,000 l 10,000,000 Overrun: 7,500,000 Overrun '

2o Bromide Br 2,900! 260,000 Exceedance 1,300 OK

L_Chloride _____ CI — Exceed ^ 1005470 12

Emission is equal to the leaching. It is the amount of component that disappears from the material on contact with water. The emission value N2 is the standard that applies to category 2 materials in the Building Materials Decree. These are materials that are slightly contaminated and may be used under separate conditions. The emission value NI is the standard for clean materials.

The mentioned E (L / S = 10) before and after washing is the amount of material that leaches in the column test.

The present invention is not limited to what has been described above; the requested rights are determined by the following claims.

1005470

Claims (19)

A method for processing waste materials such as fly ash, asphalt material and the like, comprising the step of mixing the waste material with one or more predetermined binders in a predetermined ratio, followed by subjecting the resulting mixture to a matrix forming step, whereby under predetermined reaction conditions, the one or more binders and the waste material react together to form a matrix, in which matrix impurities present in the waste material are substantially immobilized in such a way that leaching of these impurities from the mixture is countered. 2. A method according to claim 1, wherein the mixture of waste material and binders is subjected to a homogenization step. A method according to claims 1 or 2, wherein the mixture is compressed, preferably in the form of briquettes, before being subjected to the matrix-forming step. A method according to claims 1, 2 or 3, wherein after the matrix-forming step, the compressed mixture is broken. A method according to any one of the preceding claims, wherein after the matrix-forming step, the mixture is washed. A method according to any preceding claim, wherein the waste material is selected from the group consisting essentially of AVI fly ash, E fly ash and asphalt filter material. A method according to any one of the preceding claims, wherein the binders are selected from the group consisting mainly of sand, lime, quicklime, and molding sand and wherein, preferably leaching additives are added, selected from the group consisting of 10054 mainly of carbon black, polymers and water repellents, preferably water glass. A method according to any preceding claim, wherein the mixture comprises 40-90 wt%, preferably 50-60 wt% and most preferably about 55 wt% waste material, and about 1-40 wt% binders, preferably 25-35 wt% binders and most preferably about 30 wt% binders. The method of claim 9, wherein the mixture comprises about 55 wt% AVI fly ash, about 6.4 wt% E fly ash, about 28.6 wt% sand and about 10 wt% lime. 10. A method according to any one of claims 3-9, 15 wherein the mixture is compressed in a briquette press under a pressure of about 5-60 kN / cm, preferably of about 10-20 kN / cm and most preferably a pressure of about 15 kN / cm. A method according to any one of claims 7-10, 20, where, when the binder is quicklime, it is quenched by adding water. 12. A method according to 11, wherein the lime is quenched with water in a temperature range of about 50-100 ° C, preferably 90-100 ° C and most preferably about 95 ° C. A method according to any preceding claim, wherein the matrix-forming step is carried out at a temperature of between about 150-250 ° C, preferably 190-200 ° C and most preferably about 195 ° C, under a pressure within the range from about 4-14 MPa, preferably 10-12 MPa over a time period of about 2-30 hours, for example 12 hours, preferably 6 hours, and most preferably about 4 hours. Material obtainable by the method according to any of the preceding claims. Material according to claim 14, which has a granular shape with an average grain size 1005470 of approximately 40 mm, preferably 30 mm and most preferably 20 mm, and which substantially complies with the standards as stated in the Building Materials Decree for soil and surface water protection. . Building material comprising a product according to claims 14 or 15. 17. Use of a product according to claim 16 as a building material, preferably as a sand substitute, wherein the product substantially complies with the civil engineering specifications as stated in the RAW standard 1995, or as aggregate in concrete. 18. System of equipment for carrying out the method according to 1-13, comprising a mixing chamber, in which a mixture is miscible and a reaction vessel, preferably an autoclave, in which the matrix-forming step is feasible. System according to claim 18, further comprising a homogenizing machine and / or a briquetting press and / or a crusher and / or a washing installation. ^ 00 547 0