EP3807216A1

EP3807216A1 - Treatment process for recycling silicon ingot cutting waste

Info

Publication number: EP3807216A1
Application number: EP19737856.5A
Authority: EP
Inventors: Yun Luo
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-06-14
Filing date: 2019-06-13
Publication date: 2021-04-21
Also published as: CN112512970A; JP7376215B2; WO2019239067A1; FR3082512A1; FR3082512B1; JP2021527027A; US20210253435A1

Abstract

The invention relates to a treatment process for purifying silicon microparticles contained in waste resulting from the cutting of ingots with a diamond wire, comprising: a) providing a contaminated slurry, resulting from said waste, formed by an aqueous mixture comprising the silicon microparticles, organic species and metal contaminants; b) adding a dilute hydrogen peroxide solution to the contaminated slurry, in order to form a first mixture, and stirring the first mixture; c) solid/liquid separation of the first mixture in order to obtain, on the one hand, a first purified slurry and, on the other hand, a first liquid loaded with organic species and metal contaminants.

Description

PROCESSING PROCESS FOR RECYCLING CUTTING WASTE

SILICON INGOTS

FIELD OF THE INVENTION

The present invention relates to the silicon production line for the photovoltaic industry. It relates in particular to a treatment process for the recycling of waste from the cutting of silicon ingots ("kerf").

TECHNOLOGICAL BACKGROUND OF THE INVENTION

Today, silicon wafers, intended for the semiconductor or photovoltaic industry, are manufactured from silicon ingots, essentially using cutting techniques using diamond wires. These processes have gradually supplanted sawing with metallic threads with abrasives (“slurry sawing” according to English terminology), because they provide better quality of inserts, at a lower production cost.

The width of the diamond wires being of the same order of magnitude as the thickness of the cut wafers, these sawing processes nevertheless generate a significant amount of silicon waste: up to 40 to 50% of the total mass of an ingot. This waste is found in the form of very fine powder (silicon microparticles whose surface is oxidized), mixed with liquid additives, metallic contaminants and organic or inorganic species.

The silicon powder, correctly extracted from this mixture and purified, could be of great value for reuse in various industries, in particular those of the photovoltaic, energy storage, ceramic synthesis, etc. Effective purification of this silicon powder must in particular fulfill the following three objectives:

• Reduction of organic species:

These species come from organic (liquid) additives used in the sawing process or from polymer compounds contained for example in diamond wires or in saws. The presence of organic species residues in the silicon powder reduces the possibilities of reuse thereof; in fact, in most cases, the silicon is subjected to treatments at high temperatures, during which the organic species will be capable of creating particles of Sic, unfavorable to the majority of applications.

• Reduction of metallic contaminants:

These contaminants mainly come from diamond wires of a metallic nature. They can exist in different forms: ionic, atomic, particulate, and be dispersed in the mixture or linked to the surface of the silicon microparticles. The presence of residues of metallic contaminants in the silicon powder negatively affects the performance of the devices developed, in particular in semiconductor and photovoltaic applications.

• Reduction of silicon oxide:

The surface of the silicon microparticles has a layer of silicon oxide which can hinder, in certain cases, their reuse.

Several methods are proposed in the prior art, for extracting and purifying the silicon microparticles from cutting waste (“kerf”), in particular described in documents WO2012125942, W02010003456, CN103373731.

Document WO2012125942 proposes a method using ozone to eliminate organic species, hydrochloric acid to dissolve metallic contaminants and hydrofluoric acid to eliminate the layer of silicon oxide. The main disadvantages of this method lie in the limited effectiveness of ozone due to its low solubility in water, and in the use of concentrated acids.

The document W02010003456 also uses concentrated acids, which can pollute the environment and generate high process costs.

Document CN103373731 proposes a method based on the oxidation of the silicon powder by a strong oxidant, followed by the extraction of the oxidized powder with an organic solvent. The disadvantages of this method lie in the use of chemicals that pollute the environment such as organic solvent and acid to deoxidize the silicon powder. The loss of part of the silicon during the process (due to its oxidation) is also significant.

Other methods propose successive treatment sequences with strong bases and with strong acids, according to processes conventionally implemented for cleaning silicon (RCA clean). Unfortunately, these cleanings, which are very effective on silicon wafers, do not make it possible to reach the level of purification required in the case of silicon microparticles dispersed in an aqueous contaminated mixture. OBJECT OF THE INVENTION

The present invention aims to overcome all or part of the aforementioned drawbacks. The invention relates to a treatment method for recycling waste from the cutting of silicon ingots ("kerf"), by sawing with diamond wires, without abrasive.

BRIEF DESCRIPTION OF THE INVENTION

The invention relates to a treatment method for the purification of silicon microparticles contained in waste resulting from the cutting of ingots by diamond wires, without abrasive, comprising:

a) the supply of a contaminated mud, resulting from said waste, formed by an aqueous mixture comprising the microparticles of silicon, organic species and metallic contaminants;

b) adding a dilute solution of hydrogen peroxide to the contaminated mud, to form a first mixture consisting of the contaminated mud, hydrogen peroxide and water, and stirring the first mixture;

c) solid / liquid separation of the first mixture to obtain, on the one hand, a first purified sludge and, on the other hand, a first liquid loaded with organic species and metallic contaminants.

According to other advantageous and non-limiting characteristics of the invention, taken alone or in any technically feasible combination:

• in step a), the contaminated sludge is obtained from the waste, by a solid / liquid separation technique chosen from sedimentation, centrifugation, cyclonic separation or filtration, and the contaminated sludge comprises approximately 50% solid matter and 50% liquid matter, in mass percentages;

• in step b), the dilute solution of hydrogen peroxide has a mass concentration of between 1% and 35%;

• step b) comprises the addition of pure water to the first mixture, so that said first mixture comprises between 5 and 10% of solid matter, in percentage by mass;

• step b) is operated at a temperature between 20 ° C and 95 ° C, for a period ranging from 10 min to 5 h;

• the solid / liquid separation of step c) is carried out by a technique chosen from filtration, sedimentation, centrifugation or cyclonic separation, and in which the first purified sludge contains at least 40% solid matter, in percentage mass;

• the treatment method comprises, after step c), a step c ') during which one operates:

o adding pure water to the first purified sludge to form a second mixture,

o solid / liquid separation of the second mixture to obtain, on the one hand, a second purified sludge and, on the other hand, a second liquid containing organic species and metallic contaminants.

• stirring is applied to the second mixture; • step c ') is repeated one to five times;

• the treatment process comprises, after step c), a step c '') during which one operates:

o the supply of the first purified sludge, maintained in the form of a filter cake,

o the circulation of a solution of hydrofluoric acid diluted between 0.1% and 1%, in percentage by mass, through the filter slab;

o circulation of pure water through the filter wafer, allowing rinsing of said wafer and elimination of hydrofluoric acid; o obtaining a third purified sludge.

• the treatment process comprises, after step c ', a step c' ') during which one operates:

o the supply of the second purified sludge, maintained in the form of a filter cake,

o circulation of pure water through the filter wafer, allowing rinsing of said wafer and elimination of hydrofluoric acid; o obtaining a third purified sludge;

• the treatment process comprises a step d) of drying a purified sludge under an inert atmosphere to obtain purified silicon microparticles.

BRIEF DESCRIPTION OF THE DRAWINGS Other characteristics and advantages of the invention will emerge from the detailed description which follows with reference to the appended figures in which:

Figure 1 shows steps of the treatment method according to the invention;

Figures 2a, 2b and 2c show an illustration of the treatment process for the purification of silicon microparticles, according to the invention; Figures 3a, 3b, 3c and 3d show sectional views of a filter pad during sequences of a step of the treatment process according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a treatment method aimed at the purification of silicon microparticles contained in waste resulting from the cutting of ingots by diamond wires, without abrasive (FIG. 1). As mentioned above, the silicon in this waste is found in the form of a very fine powder (silicon microparticles at least partially oxidized on the surface), mixed with liquid additives, metallic contaminants and organic or inorganic species. This waste mainly contains liquid matter, the mass percentage of silicon (which constitutes the majority of solid matter) is between 2% and 5%.

The treatment method according to the invention comprises a step a) consisting in the supply of a contaminated sludge, coming from sawing waste, formed by the microparticles of silicon, organic species and metallic contaminants in an aqueous mixture. Generally, microparticles of silicon have a size distribution between about 10 nm and 5 microns, typically centered on 1 micron.

In the following description, we will use the name "mud" to describe a substance comprising more than 40% (mass percentage) of solid material (mainly consisting of silicon microparticles), mixed in an aqueous solution. All the proportions relating to the sludge of the present description are given in percentages by mass.

Advantageously, in step a), the contaminated sludge comprises approximately 50% of solid material and 50% of liquid material. The term “approximately” here means that the value of the mass percentage is +/- 10% (absolute: that is to say that a mass percentage of approximately 50% may vary between 40% and 60%), or even +/- 5% (absolute). Contaminated sludge can be obtained from cutting waste (composed essentially of liquid material, the mass percentage of silicon being between 2% and 5%), by a known method of solid / liquid separation chosen from filtration (for example vacuum filtration) or tangential filtration, sedimentation, centrifugation or cyclonic separation. The contaminated sludge thus obtained has more than 40% solid matter (percentage by mass).

The treatment method according to the invention then comprises a step b) during which a dilute solution of hydrogen peroxide (H2O2) is added to the contaminated sludge, thus forming a first mixture. By dilute solution is meant a solution consisting of hydrogen peroxide and water. The diluted hydrogen peroxide solution may have a mass concentration of between 1% and 35% of hydrogen peroxide, the additional percentage being water. Note that no other acidic or basic product is added to form the first mixture. The first mixture therefore consists of contaminated mud, hydrogen peroxide and water.

The respective proportions of dilute solution and contaminated sludge in the first mixture will depend on the concentration of H2O2. By way of example, for a H 2 O 2 concentration of 35%, the first mixture preferably comprises a volume of dilute H 2 O 2 solution for a volume of contaminated sludge; for a concentration of H 2 O 2 of 10%, the first mixture preferably comprises three volumes of diluted solution for one volume of contaminated sludge.

Step b) also includes the stirring of this first mixture, so as to homogenize the distribution of the dilute H 2 O 2 solution in the middle of the silicon microparticles 1 and other organic species 3 or metallic contaminants 4.

The silicon microparticles 1 originating from the contaminated sludge mainly comprise a layer of silicon oxide 2 on their surface; moreover, they are totally or partially “covered” by layers formed by long chains of organic species 3 (FIG. 2a). Hydrogen peroxide, by an oxidation reaction of organic species 3, will induce the segmentation of long organic chains 3 which favors their detachment from the surface of silicon microparticles 1. Consequently, metallic contaminants 4, linked to the silicon microparticles 1 via the organic layers 3, will also be detached (Figure 2b). Note that this oxidation reaction also generates carbon dioxide (C02) in gaseous form.

Advantageously, the first mixture comprises approximately 5% to 10% of solid material and an additional percentage of liquid material (in mass percentage): this liquid consistency promotes the suspension of silicon microparticles 1 and other organic species 3 or metallic contaminants 4, in the first mixture. Note that the term "approximately" is defined as stated above.

Such consistency of the first mixture is directly reached when a solution with a low concentration of H 2 O 2 is mixed with the contaminated sludge. In the case of solutions with a higher concentration of H 2 O 2 (for example between 10 and 35%), the volume of diluted H 2 O 2 solution added is not sufficient to reach 5% to 10% of solid matter in the first mixture, pure water is added to achieve the desired consistency of said first mixture. By pure water is meant deionized water or ultra-pure water, respectively having a resistivity of a few hundred kohms. cm and a resistivity greater than 18.2 Mohms.cm.

The agitation of the first mixture then makes it possible to homogenize the distribution of the microparticles of silicon 1 and other organic species 3 or metallic contaminants 4 suspended in the first mixture; stirring also makes it possible to increase the efficiency of the oxidation reaction segmenting the organic chains 3.

Step b) can be carried out at a temperature between 20 ° C and 95 ° C, for a period ranging from 10 min to 5 h.

At the end of step b), the first aqueous mixture comprises particles in homogeneous suspension, among which the silicon microparticles 1, the organic species 3 mainly in the form of segmented chains and the metallic contaminants 4.

The treatment method according to the invention then comprises a step c) implementing a solid / liquid separation of the first mixture to obtain, on the one hand, a first purified sludge and, on the other hand, a first liquid loaded with organic species and metallic contaminants. The first purified sludge is composed of at least 40% solid matter (Figure 2c). The first liquid can be discharged and treated as a liquid effluent.

Due to the segmentation of organic chains, fragments of organic layers are detached from the silicon microparticles (step b)) and they are, in step c), removed with the liquid part (first liquid), due to their reduced size and / or their dissolution in water, and therefore separated from the solid material (first purified sludge).

The Applicant has found that after step c) of solid / liquid separation at least 90% of the organic species initially present in the contaminated sludge are discharged into the first liquid. The metallic contaminants (all combined), initially present at approximately 1% to 3% (mass percentage) in the contaminated sludge are also greatly reduced after this step c), in particular due to their initial bond with organic species.

The solid / liquid separation technique of step c) may be chosen from sedimentation, centrifugation, cyclonic separation, filtration, or other suitable known technique.

Advantageously, the treatment process comprises a rinsing step c ', during which pure water is added to the first purified sludge to form a second mixture (Figure 1). The second mixture preferably comprises at least ten volumes of water for a volume of the first mud. Agitation is provided to homogenize the second mixture.

Step c ′) then comprises a solid / liquid separation of the second mixture to obtain, on the one hand, a second purified sludge and, on the other hand, a second liquid containing organic species and residual metallic contaminants. The second purified sludge is composed of at least 40% solid matter. Like the first liquid, the second liquid can be discharged and treated as a liquid effluent.

This second purified sludge is rinsed once more than the first sludge. It therefore has a higher level of purity: at least 95% of the organic species initially present in the contaminated sludge are eliminated after this step c '). The level of metallic contaminants is also improved following this step c ').

Advantageously, step c ′) is repeated one to five times, in order to reach an optimal level of purity (typically a reduction in organic species and metallic contaminants by at least a factor of one hundred compared to the initial contaminated sludge), all by keeping costs (generated by the repetition of step c ')) reasonable.

The treatment method according to the invention advantageously comprises a step d) during which a purified sludge (the first or the second) is dried under an inert atmosphere, so as to obtain purified silicon microparticles.

Preferably, the drying is carried out under vacuum, at a temperature between 50 ° C and 80 ° C and with stirring. Equipment of the filter-dryer type, fitted with a mechanical stirrer, may for example be used. At the end of the treatment process, a very good level of purification (organic and metallic) of the silicon microparticles is typically reached:

• Less than 0.3% (mass) of carbon;

• Less than 100 ppm (mass) of metallic contaminants (all combined).

And this, without the use of highly polluting products such as bases and concentrated acids used in the processes of the prior art.

The silicon microparticles nevertheless retain an oxide layer on their surface.

According to a variant, the treatment method according to the invention comprises a step c '') intended to remove all or part of the oxide present on the silicon microparticles. Step c '') can be carried out after step c) or after step c ') (Figure 1).

It includes first of all the supply of the first 11 (or of the second 12) purified sludge, maintained in the form of a filtration wafer 10 (FIG. 3a). A filter cake 10 can in particular be obtained after filtration under a press (“filter-press cake” according to English terminology): the first 11 (or the second 12) purified mud is thus kept pressed between two porous membranes 20, taking the shape of a pancake 10.

Step c '') then comprises circulating a solution 30 of hydrofluoric acid (HF) diluted between 0.1% and 1% (mass percentage) through the filter slab 10 (FIG. 3b). The HF solution 30 will thus be in contact with the silicon microparticles of the wafer 10 and attack the oxide layer surrounding them, all along its path between the two membranes 20. For example, for a volume of wafer 10, two volumes of 0.5% HF 30 solution will be circulated. For a lower HF concentration, a higher number of volumes of solution 30 will be used to cross the wafer 10.

Then, step c '') comprises the circulation of pure water 40 through the filtration wafer 10 allowing the rinsing of said wafer 10 and the elimination of hydrofluoric acid (FIG. 3c). Indeed, the pure water 40 will circulate through the wafer 10 by taking more or less the same paths and interstices as the HF solution 30, thus ensuring an effective rinsing of said wafer 10. For example, for a volume of wafer, ten volumes of pure water 40 will be circulated through the wafer 10. A pH measurement at the level of the water outlet membrane makes it possible to check the effectiveness of the rinsing: a pH value of 7 is targeted for a complete rinsing.

Step c '') ends with obtaining a third purified sludge 13 (Figure 3d), composed of more than 40% solid material. The third purified sludge 13 is formed from silicon microparticles predominantly devoid of their surface oxide layer.

According to this variant, the treatment method advantageously comprises a drying step d) during which the third purified sludge is dried under an inert atmosphere to avoid the formation of an oxide layer on the purified silicon microparticles.

The conditioning which follows this step is also carried out so as to keep the dry silicon powder in an inert, non-oxidizing atmosphere.

At the end of the treatment method according to this variant, purified silicon microparticles with a low silicon oxide content are obtained; they may have the following characteristics:

• Less than 1% (mass) of oxygen,

• Less than 0.3% (mass) of carbon, • Less than 50 ppm (mass) of metallic contaminants (all combined); note that step c '') of oxide removal makes it possible to lower the level of metal contaminants because these are often integrated into the surface oxide layer covering the silicon microparticles: the elimination of this layer promotes therefore the elimination of metallic particles.

Such characteristics make the silicon powder compatible with the majority of applications, and in particular with the photovoltaic industry.

The treatment method according to the invention allows recycling of more than 95% of the silicon contained in the form of microparticles in sawing waste.

Of course, the invention is not limited to the embodiments described and it is possible to make variant embodiments without departing from the scope of the invention as defined by the claims.

Claims

1. Treatment process for the purification of silicon microparticles contained in waste resulting from the cutting of ingots by diamond wires, comprising:

2. Treatment method according to the preceding claim, in which, in step a), the contaminated sludge is obtained from the waste, by a solid / liquid separation technique chosen from sedimentation, centrifugation, cyclonic separation or filtration, and the contaminated sludge comprises approximately 50% solid matter and 50% liquid matter, in mass percentages.

3. Treatment method according to one of the preceding claims, in which, in step b), the dilute hydrogen peroxide solution has a mass concentration of between 1% and 35%.

4. Treatment method according to one of the preceding claims, in which step b) comprises the addition of pure water to the first mixture, so that said first mixture comprises between 5 and 10% solid matter, in percentage mass.

5. Treatment method according to one of the preceding claims, in which step b) is carried out at a temperature between 20 ° C and 95 ° C, for a period ranging from 10 min to 5 h.

6. Treatment method according to one of the preceding claims, in which the solid / liquid separation of step c) is carried out by a technique chosen from filtration, sedimentation, centrifugation or cyclonic separation, and in which the first purified sludge contains at least 40% solid matter, in percentage by mass.

7. Treatment method according to one of the preceding claims, comprising, after step c), a step c ') during which one operates:

• adding pure water to the first purified sludge to form a second mixture,

• solid / liquid separation of the second mixture to obtain, on the one hand, a second purified sludge and, on the other hand, a second liquid containing organic species and metallic contaminants.

8. Treatment method according to the preceding claim, wherein step c ') is repeated one to five times.

9. Treatment method according to one of claims 1 to 6, comprising, after step c), a step c '') during which one operates:

• the supply of the first purified sludge, maintained in the form of a filter cake,

• the circulation of a solution of hydrofluoric acid diluted between 0.1% and 1%, in percentage by mass, through the filter slab;

• circulation of pure water through the filter wafer, allowing rinsing of said wafer and elimination of hydrofluoric acid;

• obtaining a third purified sludge.

10. Treatment method according to one of the preceding claims, comprising a step d) of drying a purified sludge under an inert atmosphere to obtain purified silicon microparticles.