• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The invention describes a method of recovering valuable substances from slag incineration of urban solid waste less than 25/30 mm. The process comprises the steps of a) recovering light metals and their alloys, iron material, heavy metals and their alloys and non-incinerated organic matter; as well as b) recover valuable minerals and ferrous and heavy metals. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2662880A1
    申请号:ES201830156
    申请日:2018-02-21
    公开日:2018-04-10
    发明作者:Eduardo FERNANDEZ JIMENEZ；Ignacio SANZ MADROÑO；Dulce GOMEZ LIMON；Ramon ALVAREZ RODRIGUEZ；Carlos GRIMA OLMEDO
    申请人:Urbaser SA；
    IPC主号:
    专利说明:

    VALUABLE SUBSTANCES RECOVERY PROCEDURE FROM ESCORIA

    Field of the Invention
    The present invention relates generally to the field of recycling of substances from urban solid waste. More specifically, it refers to a procedure for recovering substances for recycling from urban solid waste incineration slags, more specifically from incineration slags 10 smaller than 25/30 mm.

    Background of the invention
    At present, the need is recognized to recover as much as possible the metals contained in waste of any kind on the one hand in order to increase security in the supply of raw materials, and on the other hand to reduce the possible contamination that may cause its deposition in landfills.
    In the art, facilities 20 for the energy recovery of MSW (urban solid waste) which in turn usually generate two types of waste are widely known: ashes from the purification of the gas stream and slags obtained directly from the furnace. The ashes are generated in a proportion of 3-5% 25 with respect to the weight of the original waste, while the slags constitute 20% of the original weight.
    Currently, these “waste” are basically deposited in landfills, although some methods are known to extract valuable substances from them for 30 recycling purposes. For example, documents CN105195313 and ES23633920 disclose methods of this type, however, they do not achieve an optimal recovery of said
    valuable substances and also involve a considerable energy expenditure due to their need to dry the slags before starting recovery methods.
    Therefore, currently in practice slag incineration of municipal solid waste less than 5 25/30 mm is usually deposited in a suitable landfill. However, this fraction still contains metals, non-incinerated organic matter, as well as valuable mineral products that on the one hand are polluting for the environment (especially because they contain heavy metals) and on the other hand it would be desirable to recover them for recycling. In fact, recycling these substances would have a double advantage: to reduce their polluting potential for the environment and at the same time favor their reuse, which would reduce their demand as a raw material of primary origin.
    Therefore, there is a need in the art to have a process for recovering valuable substances from slag from incineration of municipal solid waste that allows the separation, recovery and recycling of metals, organic matter and mineral substances as much as possible. thus converting waste usually deposited in landfills into new raw materials. Furthermore, it would be desirable that said recovery procedure can be carried out with the lowest possible energy consumption.

    Summary of the invention
    To solve the problems of the prior art, the present invention discloses a method of recovering valuable substances from slag incineration of urban solid waste smaller than 25/30 mm. The procedure comprises the steps of:
    a) recover light metals and their alloys, iron material, heavy metals and their alloys and non-incinerated organic matter; Y
    b) recover valuable minerals and ferrous and heavy metals. 5

    Brief description of the drawings
    The present invention will be better understood with reference to the following drawings illustrating a preferred embodiment of the present invention, provided by way of example, and which should not be construed as limiting the invention in any way:
    Figure 1 shows a flow chart of step a) according to the preferred embodiment of the present invention. fifteen
    Figure 2 shows a flow chart of step b) according to the preferred embodiment of the present invention.
    Figure 3 shows a flow chart of step c) according to the preferred embodiment of the present invention.
     twenty
    Detailed description of the preferred embodiments
    According to a preferred embodiment of the present invention, a process for recovering valuable substances from slag incineration of urban solid waste smaller than 25/30 mm is disclosed. The method according to this preferred embodiment comprises the steps of:
    a) recover light metals and their alloys, iron material, heavy metals and their alloys and non-incinerated organic matter; 30
    b) recover valuable minerals and ferrous and heavy metals; and optionally
    c) purify and recirculate the water used in the various stages and sub-stages of the procedure.
    As used herein, the term "purify" refers to "improve the quality" of the water so that it can be recirculated to the process. It should not be understood as a complete removal of all impurities that may be present in said process water.
    The incineration slags of urban solid waste less than 25/30 mm that are used as raw material in the process according to the present invention are generally in a wet state. According to the preferred embodiment of the present invention, the process is carried out entirely by wet means, that is, it is not necessary to dry the slags received before carrying out the process of the present invention. In this way, the energy expenditure is reduced in comparison with other procedures for recovering substances from slags that must be carried out dry, and therefore the overall economic cost of the process is reduced.
    Each of the steps a), b) and c) will now be described in more detail with reference to Figures 1, 2 and 3, respectively.
    As can be seen in Figure 1, optionally the scum received is initially subjected to an initial washing and screening, for example, in a 25/30 mm scrubber and screener cylinder.
    Next, the 25/30 mm slag fraction is subjected to a sub-stage a-1) of grinding / crushing selectively by a single stage, or by two, three or four successive stages using crushing apparatus
    or milling of smooth cylinders or pressure cylinders, preferably with intermediate screens at suitable sizes to finish obtaining a fraction of size greater than about 0.5 / 1 mm of intrillables and a size fraction of less than 0.5 / 1 mm. In a sub-stage a-2), the size fraction smaller than 0.5 / 1 mm is sent to step b), which will be described hereinafter.
    In a sub-stage a-3), the previous fraction of size greater than 0.5 / 1 mm of intrusible 10 is floated in water in a separator that allows most of the organic matter to float and separate (for example, a drum or separating cone or screw classifiers, racletas, etc.). Said organic matter is drained and recycled to the previous incineration, dried, dried, etc. fifteen
    In sub-stage a-3) metals and alloys are also obtained that sink and pass to the next sub-stage a-4), in which they are subjected to magnetic separation by means of a low intensity magnetic separator of roller, tape, etc., to obtain a material of iron and other 20 metals and light and heavy alloys. Iron material can be sold for recycling.
    In sub-stage a-5), light and heavy metals and alloys from sub-stage a-4) are subjected to gravimetric separation by density, using, for example, a system of dense media with a density close to 2.9 / 3 g / cm3, which allows to obtain a fraction of metals and light alloys and a fraction of metals and heavy alloys, both of which can be recycled. 30
    According to a preferred embodiment, the fraction of metals and light alloys obtained in sub-stage a-5) comprises aluminum, magnesium, alloys based on the
    themselves and mixtures thereof, which can be sold for recycling.
    On the other hand, the fraction of metals and heavy alloys obtained in sub-stage a-5) preferably comprises copper, zinc, lead, tin, base alloys thereof and mixtures thereof, and possibly a certain amount of non-stainless steel. magnetic. This fraction is also valuable and can be recycled properly.
    Referring now to Figure 2, a preferred embodiment of step b) of the process of the present invention will be described in more detail, which is carried out with the size fraction smaller than 0.5 / 1 mm obtained in the sub-stage. a-1) described above.
    Thus, in the sub-stage b-1), the size fraction smaller than 0.5 / 1 mm from the previous sub-stage a-1) is subjected to magnetic separation in a low intensity magnetic concentration system with type devices cylinder, tape, etc. In this way, by means of roughing, depleted or relaxed phases (if necessary with intermediate shaking and rewiring) a concentrate of valuable magnetic mineral, preferably magnetite, is obtained, which can be sold or recycled as iron ore, as a high capacity material. heating for deferred heating systems, etc. 25
    In this sub-stage b-1) a non-magnetic fraction is also obtained that advances towards the next sub-stage b-2), in which a gravimetric separation by density thereof is carried out, for example in concentration tables, spirals, etc. , to obtain a dense concentrate 30 and a fraction of light material.
    The fraction of lightweight material, which is the bulk of the treated material but already free of most of the
    metals, especially heavy ones, are drained and can be deposited in a landfill with a polluting potential substantially lower than the original slag.
    For its part, the dense concentrate is preferably composed of dense metals such as copper, lead, tin, etc., alloys thereof and mixtures thereof, as well as some heavy minerals such as magnetite residues. This dense concentrate is subjected, in a sub-stage b-3), to a magnetic separation in a magnetic separator to obtain a normally low quality magnetic product and a non-magnetic fraction enriched in heavy metals.
    The magnetic product can go to landfill or, if necessary, be reintroduced into the incinerator to try to recycle it. The non-magnetic fraction is highly enriched in heavy metals and can be sold for recycling.
    Therefore, the process according to the preferred embodiment of the present invention comprising steps 20 a) and b) above allows the recovery of valuable substances from incineration slag (metals and light and heavy alloys, iron material, valuable minerals such as magnetite, etc.) as well as the disposal to landfill of waste with less potential for polluting the environment. On the other hand, the process according to the preferred embodiment of the present invention has a high energy efficiency since it is carried out entirely by the wet route, without requiring any drying of the slag starting prior to the implementation of the recovery procedure.
    Furthermore, according to a more preferred embodiment of the present invention, the method comprises the step
    optional c) (see Figure 3) to purify and recirculate the water used in the various stages and sub-stages of the process. Specifically, in a stage c-1), all the waters used in the washes, screens, magnetic or gravimetric separations, etc. are collected. and 5 are subjected to a hydrocyclone and drained to obtain solids to be deposited in landfill and water.
    Then, in the sub-stage c-2), the water from the sub-stage c-1) is decanted in a decanter in which, with the appropriate use of flocculants if necessary, the solid material that is going is decanted in suspension to obtain water and a thick suspension. The water obtained at this stage can be recirculated directly to the process of the present invention.
    On the other hand, the thick suspension is subjected to a subsequent filtration that allows to obtain a solid cake that can be deposited in landfill, as well as water that is recirculated towards the sub-stage c-2) of decantation.
    If the water has a pH too high between the sub-stages c-1) and c-2), it can be reduced by adding 20 CO2 either directly or from the combustion fumes of the incinerator. It should be borne in mind that a certain alkalinity is even beneficial for the equipment with respect to the corrosion control of the equipment. 25

    Example
    Having described in detail a preferred embodiment of the present invention, an example of a specific application thereof will be described below. 30
    It should be borne in mind that the data, especially the percentages by weight of the final fractions obtained can vary significantly with each sample since the
    Initial substance, which is urban solid waste, shows a great variability of composition with the place of origin, and also with time.
    Slag was used as raw material from the incineration of municipal solid waste that had a humidity of 23.51%. Table 1 below shows the result of a chemical analysis performed with a sample of said starting slag, while table 2 shows the results of a granulometric analysis thereof. 10

    Table 1: Chemical analysis of the starting slag
     Majority Elements  %  SiO2  33.20  Al2O3  6.71  Fe2O3  10.80  CaO  21.70  TiO2  0.58  MnO  0.08  K2O  0.96  MgO  1.66  P2O5  0.68  Na2O  4.12  SO3  1.75  Cl  0.69  PPC 900 ° C  11.00  Trace elements  ppm  Cr  267  Co  25  Neither  79  Cu  3686
     Zn  2965  Ace  <5  CD  9  Sn  223  Sb  81  Pb  4236


    Table 2: Granulometric analysis of the starting slag
     Size, mm  Weight, %  > 16  1.82  > 8  6.06  > 4  11.39  > 2  17.48  > 1  17.77  > 0.5  12.73  > 0.25  7.47  > 0.125  4.85  > 0.063  3.15  Background  17.28  SUM  100

    First, the starting slag was subjected to a differential crushing based on the fact that using machines that operate under compression, the metals present are not crushed or split, but are laminated, which even increases their apparent size. On the other hand, the stone materials do crush and diminish of 10 size, with what a later screening will allow to separate the metallic particles of mechanical form. Those substances of an organic type that do not split under pressure will also be separated.
    Then, starting from the larger fraction obtained from the previous screening, the separation between metallic and organic substances was performed by water flotation. In this way, most of the organic matter floats in the water while the 5 metallic substances sink. Organic matter separated in this way can be recycled by sending it directly to the incineration process.
    Subsequently, the metallic substances obtained were classified as magnetic and non-magnetic, and subsequently the non-magnetic substances were classified as heavy and light. Magnetic substances can be recycled and sold as iron scrap. Non-magnetic substances, separated into light ones (for example based on aluminum) and heavy ones, can also be recycled and have commercial value.
    Below are the results obtained, expressed as a percentage with respect to the dry all-one:
    - Intricable substances grouped:
    Organic substances ............................ 0.45% 20
    Magnetic substances .......................... 0.61%
    Light non-magnetic substances ................ 0.72%
    Heavy non-magnetic substances ................ 0.34%

     In Table 3 below, the analysis 25 of the heavy non-magnetic fraction is presented as indicative of the elements it may contain. Thanks to the method applied according to the present invention, said heavy elements can be recovered (they are not deposited in the landfill) and therefore the contamination can be reduced:

    Table 3: Chemical analysis of the non-intrillable fraction
    heavy magnetic
     Elements  %  Cu  66.35  Zn  21.83  Ace    0.005  CD    0.039  Sn   0.69  Sb   0.06  Pb  10.64

     On the other hand, based on the fraction of smaller size (smaller than 1 mm) obtained from the previous screening, a magnetic separation was performed by an industrial drum machine 5 of the countercurrent type, which sacrifices somewhat the recovery in exchange for obtaining a Better concentrate quality.
    Once the first concentration was made, the non-magnetic product was treated again in the same machine to give a second sweeping concentrate or rush, which in principle will be of worse quality. To investigate the losses in fines that overflow from the machine carried by the water flow, at the exit of the overflow of the sweep separation, a magnetic trap 15 formed by a bar of permanent magnets of high intensity of rare earths was placed.
    After performing these operations, the following results were obtained, expressed as a percentage with respect to the all-one: 20
    - Main or roughing magnetic concentrate: 5.65%
    - Sweeping concentrate: ......................... 0.22%
    In the concentrates some magnetic wires were collected, which were separated by 1 mm screening and chosen manually and that looked more or less broken staples. 25
    The quantities were minimal, of the order of 0.005%.
    Table 4 shows the results of a granulometry study carried out with the previous roughing and sweeping concentrates:
     5
    Table 4: Granulometric analysis of roughing and sweeping concentrates
     Size, mm  Conc. Of roughing,% by weight Conc. Of sweeping,% by weight  > 1    0.33 0.57  > 0.5   61.21 54.48  > 0.25   24.55 26.47  > 0.125    8.84 10.96  > 0.063    3.17 4.65  <0.063    1.90 2.87  TOTAL        100 100

    Table 5 below shows the result of a chemical analysis performed with these concentrates. 10

    Table 5: Chemical analysis of roughing and sweeping concentrates
     Elements,%  Conc. Of roughing Expressed as elements Conc. Of sweeping Expressed as elements  SiO2  6.05 2.83 14.11 6.50  Al2O3  1.34 0.71 2.87 1.52  Fe2O3  86.42 60.45 69.27 48.45  CaO  5.42 3.87 9.59 6.85  TiO2  0.44 0.26 0.51 0.31  MnO  0.33 0.26 0.27 0.21  K2O  <0.1 <0.08 0.40 0.33
     MgO  0.33 0.20 1.02 0.62  P2O5  0.28 0.12 0.55 0.24  Na2O  0.66 0.49 1.56 1.16  SO3  0.55 0.22 0.55 0.22  PPC 900 ° C  -5.18 -1.17  V  14  Cr  620  Co  310  Neither  750  Cu  1080  Zn  1560  CD  <2  Mo  2. 3  Ace  26  Pb  320  Sb  65

    The magnetic scanning concentrate only represents 0.22% by weight with respect to the all-one and also its quality is not good since it only reaches 48.45% in iron (expressed as Fe). It could be recirculated at the beginning or 5 taken to landfill.
    The first or roughing magnetic concentrate, obtained directly from the ground sample at <1 mm, has a better iron grade that is 60.45% expressed as metal (Fe). 10
    Subsequently, the sample was divided into two granulometric fractions, a fraction greater than 0.5 mm and a fraction smaller than 0.5 mm, and analyzed separately to see the influence of the granulometry of the concentrate. The fraction less than 0.5 mm improved in law by 15 which was decided to grind to less than 0.5 mm and return to
    magnetically concentrate, that is, make a relaxed. The results of the analysis of this concentrated concentrate are shown in Table 6. Its recovery in weight was 4.72%.
     5
    Table 6: Chemical analysis of the concentrate concentrated before grinding at <0.5 mm
     Elements,%  Conc. Of rewash Expressed as elements  SiO2  5.11 2.39  Al2O3  1.04 0.55  Fe2O3  89.96 62.92  CaO  4.40 3.14  TiO2  0.39 0.23  MnO  0.317 0.25  K2O  0.12 0.10  MgO  0.40 0.24  P2O5  0.25 0.11  Na2O  0.54 0.40  SO3  0.35 0.14  PPC 900 ° C  -4.03  V  130  Cr  637  Co  268  Neither  794  Cu  962  Zn  1373  CD  <1  Mo  2. 3  Ace  26  Pb  261
     Sb  65

    As can be seen in Table 6 above, there is a notable increase in the concentration of iron in the milling concentrate concentrate of 0.5 mm, which increases to 62.92% in metallic Fe, very close to values 5 that They are usually found in commercial products.
    In order to improve this concentrate and reduce the possible mixed grains, it is possible to re-relieve or re-concentrate this pre-ground concentrate 10 milling at <0.25 mm, since it is in the thickest fractions in which the content of mixed.
    All grains of granulometry between 1mm and <0.5mm can be subsequently concentrated on a shaking table to obtain a dense concentrate. This dense concentrate can then be separated magnetically, and the non-magnetic dense part, which represents 2.46% of the initial weight, has a grade of 5% Cu, 2.4% Zn, 0.4% Sn and 1 , 5% Pb. These metals can be recovered from this fraction by physical or hydrometallurgical methods. twenty
    As described above, the process for recovering valuable substances from slag from incineration of urban solid waste of the present invention allows to separate, recover and recycle to a large extent metals, even less than 1 mm in size, organic matter and substances minerals, turning into new raw materials residues usually deposited in landfills and at the same time reducing considerably the load of the polluting substances in comparison with the prior art. The present procedure also allows the magnetite to be recovered, which until now could not be carried out so efficiently because it has a size of
    Very low release generally of the order of 1 mm or less. In addition, it is a procedure that can be carried out with lower energy consumption compared to existing procedures.
    Although a detailed description 5 of preferred embodiments of the present recovery procedure has been provided, the person skilled in the art will understand that modifications and variations can be applied thereto without thereby departing from the scope of protection of the present invention, defined exclusively by the claims. 10 attached.
    权利要求:
    Claims (18)
    [1]
    1. Procedure for the recovery of valuable substances from slag incineration of municipal solid waste less than 25/30 mm, which includes the stages of:
    a) recover light metals and their alloys, iron material, heavy metals and their alloys and non-incinerated organic matter; Y
    b) recover valuable minerals and ferrous and heavy metals.
    [2]
    2. Method according to claim 1, characterized in that it is carried out by the wet route.
    [3]
    3. Method according to any of the preceding claims, characterized in that the valuable minerals recovered in step b) consist of magnetite.
    [4]
    4. Method according to any of the preceding claims, characterized in that the substances recovered in step a) have a size greater than 0.5 / 1 mm.
    [5]
    5. Method according to any of the preceding claims, characterized in that the substances recovered in step b) have a size smaller than 0.5 / 1 mm.
    [6]
    Method according to any of the preceding claims, characterized in that step a) comprises the sub-stages of:
    a-1) selectively grind / crush the slag and separate by screening to obtain a size fraction of less than 0.5 / 1 mm and a size fraction of greater than 0.5 / 1 mm;
    a-2) send the size fraction less than 0.5 / 1 mm to
    stage b);
    a-3) flotation in water the fraction of size greater than 0.5 / 1 mm to obtain floating organic matter and sinking metals and alloys;
    a-4) subject sunken metals to low density magnetic separation to obtain recycled iron material and other light and heavy metals and alloys; Y
    a-5) subject to gravimetric separation by density the light and heavy metals and alloys from sub-stage a-4) to obtain a fraction of metals and light alloys and a fraction of metals and heavy alloys, both of which can be recycled.
    [7]
    7. Method according to claim 6, characterized in that the sub-stage a-1) is repeated 2 to 4 times by performing intermediate screening between each repetition.
    [8]
    8. Method according to any of claims 6 and 7, characterized in that it further comprises drying and recycling the organic matter obtained in the sub-stage a-3) towards the incineration.
    [9]
    9. Method according to any of claims 6 to 8, characterized in that the fraction of metals and light alloys obtained in the sub-stage a-5) is selected from the group consisting of aluminum, magnesium, alloys based on them and mixtures thereof. same.
    [10]
    Method according to any one of claims 6 to 9, characterized in that the fraction of metals and heavy alloys obtained in sub-stage a-5) is selected from the group consisting of copper, zinc, lead, tin, alloys based on them. and mixtures thereof.
    [11]
    Method according to any of the preceding claims, characterized in that step b) comprises the sub-stages of:
    b-1) perform a magnetic separation of a fraction of size less than 0.5 / 1 mm from stage a) to obtain a concentrate of valuable magnetic mineral and a non-magnetic fraction;
    b-2) subject to gravimetric separation by density the non-magnetic fraction from the sub-stage b-1) to obtain a dense concentrate and a fraction of light material to be deposited in landfill; Y
    b-3) subject the dense concentrate from sub-stage b-2 to low intensity magnetic separation to obtain a magnetic product and a non-magnetic fraction enriched in heavy metals to be recycled.
    [12]
    12. Method according to claim 11, characterized in that the valuable magnetic mineral obtained in the sub-stage b-1) comprises magnetite.
    [13]
    13. Method according to any of claims 11 and 12, characterized in that the sub-stage b-1) comprises intermediate rewinding and rewiring.
    [14]
    14. Method according to any of claims 11 to 13, characterized in that the dense concentrate of the sub-stage b-2) is selected from the group consisting of copper, lead, tin, alloys thereof and mixtures thereof.
    [15]
    15. Method according to any of the preceding claims, characterized in that it further comprises the step of:
    c) purify and recirculate the water used in the various stages and sub-stages of the procedure.
    [16]
    16. Method according to claim 15,
    characterized in that step c) comprises the sub-stages of:
    c-1) subject the water to hydrocycloning and draining to obtain solids to be deposited in landfill and water;
    c-2) decanting water from the sub-stage c-1) to obtain water to recirculate in the process and a thick suspension; Y
    c-3) filter the thick suspension from the sub-stage c-2) to obtain a solid cake to be deposited in landfill and water to be recirculated to the sub-stage c-2) settling.
    [17]
    17. Method according to claim 16, characterized in that the sub-stage c-2) comprises using flocculants.
    [18]
    18. Method according to any of claims 16 and 17, characterized in that it further comprises reducing the pH of the water from the sub-stage c-1) before its decantation in the sub-stage c-2).
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    同族专利:
    公开号 | 公开日
    ES2662880B2|2018-10-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1447138A1|2003-02-14|2004-08-18|Gerhard Scherer|Treatment from slags coming from waste combustion installations|
    CN102489491A|2011-12-07|2012-06-13|天津康斯明节能环保科技有限公司|System and process for recycling furnace slag|
    CN202316501U|2011-12-07|2012-07-11|天津康斯明节能环保科技有限公司|Recycling system of furnace clinkers|
    CN106623353A|2016-11-16|2017-05-10|小威环境（北京）科技有限公司|Method for producing recycled aggregate from household garbage incineration slag|
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