FR2664611A1 - PROCESS FOR THE PRODUCTION OF AGGLOMERS AND PRODUCTS OBTAINED - Google Patents

Abstract

The invention relates to a process for the manufacture of agglomerates by compression and heating of a mixture of fines, powders, granules, based on carbonaceous materials, in particular on fuels or based on ores, a binder, optionally of other additives, characterized in that the binder is a system comprising at least one molasses and at least one molasses catalyst, chosen from organic or inorganic ammonium salts. The process is advantageously applied to the manufacture of combustible agglomerates in the form of briquettes, balls, etc.

Description

PROCESS FOR THE MANUFACTURE OF AGGLOMERS AND PRODUCTS

OBTAINED.

  The present invention relates to the manufacture of ag-

  glomerates, in particular agglomerates based on solid materials

  fuels, or ores It concerns more specifically

  Firstly, a process for agglomerating these materials in the form of powders, fines or granules by using a new system of low-sulfur binder, as well as the products obtained. There are many methods of agglomeration for

  forming briquettes or other agglomerates based on

  solid fuels such as charcoal, anthracite, coke

  use binders or other additives

  increase the cohesion of the agglomerates and must preserve this cohesion in the storage conditions at

  outside and especially in the presence of water.

  In addition, the binders must have suitable properties during the combustion of the agglomerate, when

  It is a question of fuel, and in particular, it must not be the source of emissions of odors and harmful gases35 for the environment.

  The binders recommended in the state of the art are, for example, bitumen, starch, alcohols

  polyvinyl alone or in the presence of lime, as de-

  in GB Patent Publication 2,138,442, a mixture of polyvinyl alcohol with molasses such as

  EP 0 135 784 describes molasses catalyzed with calcium salts, phosphates as described in GB 230306, or black liquors from paper mills with dichromate and sodium hydroxide. sulfuric acid, as described in the literature.

  EP 0 127 351, molasses with black liquors as described in patent publication CA 1 113 246.

  The various processes and binders mentioned above are not entirely satisfactory, either they emit too many harmful odors or gases during the combustion of the agglomerates, or they do not provide sufficient mechanical or chemical resistance properties, In particular resistance to prolonged immersion in water or crush resistance,

  this is particularly the case for processes using molasses as a binder. The invention obviates the drawbacks cited.

  provides a process for the manufacture of agglomerates using a binder system which provides good mechanical properties

  The process according to the invention uses compression and heating agglomeration of fines, powders, powders and the like, which are suitable for the combustion of agglomerates in the case of fuels. granules, based on carbonaceous materials, in particular fuels such as charcoal, anthracite, coke, or based on ores or other minerals, a binder system comprising at least one binder chosen from molasses, and at least one hardening catalyst agent of the chosen molasses

  among organic or inorganic ammonium salts.

  The organic or inorganic ammonium salts whose catalytic action hardener vis-à-vis the molasses had never been described before, yet provide in association with this molasses a binder system

  particularly efficient and presenting all

  essential properties desired for the manufacture of agglomerates

  merged, in particular combustible agglomerates.

  In one aspect of the invention, the binder system is used at about 5 to 20% by weight

  in relation to the total weight of the agglomerate.

  The invention also relates to an agglomerated product comprising from 80 to 95% by weight of fines, powders or granules to be agglomerated based on carbonaceous materials, in particular fuels such as charcoal, anthracite, coke or other minerals, and 20 to 5% by weight of the binder system comprising at least one molasses and at least one organic or inorganic ammonium salt as a catalyst

molasses.

  The molasses forming the binder proper according to the invention may be molasses of cane or

  These molasses may be used alone or in admixture with one another or with other binders such as lignosulphonates, in particular ammonium lignosulphonate, black liquors. The catalyst of the binder system used in the process according to the invention serves, in particular, to render

  the binder, that is to say the molasses or molasses, insoluble in water.

  The organic or inorganic ammonium salts used as catalysts may be an acetate,

  carbonate, chloride, nitrate, sulfate, phosphate, ammonium lignosulfonate Advantageously, it is possible to use an ammonium lignosulfonate or ammonium nitrate.

  The weight ratio between the binder itself and the catalyst depends on the choice of the catalyst used.

  When the catalyst is ammonium lignosulfonate

  the binder system consists of about 40 to 90% of molasses and 60 to 10% of ammonium lignosulfonate.

  When the catalyst is ammonium nitrate, it can be used in a smaller amount, from about 0.5% by weight up to about 30% by weight relative to

the weight of the binder system.

  The fines, powders or granules which can be agglomerated by the process according to the invention are especially based on combustible materials such as charcoal, anthracite or coke. These can also be fines based on ores.

  4 such as nickel ores, chromite or ferro-manganese

  nese, magnesium or other minerals such as fluorspar. A particularly advantageous agglomerated product according to the invention is a product based on combustible materials such as charcoal, anthracite, coke. This agglomerated product according to the invention can be in the form of briquettes, balls, etc. It is smoke-free when of its use, insoluble and low sulfur content. To form the agglomerate, it suffices according to the invention to bring the fines into contact with the binder system,

  a temperature and for a period of time sufficient to

  the polymerization of the binder system, in particular at a temperature of between 100 and 3000 C during a

  duration of about 3 minutes to about 3 hours.

  To mix the three essential components forming the agglomerate, namely the material to be agglomerated, the binder and

  the catalyst, it is possible to premix the two components forming the binder system beforehand, and then to mix with the material to be agglomerated.

  In a variant, it is possible to carry out the premixing of the

  material to be agglomerated with the catalyst.

  We can still mix the three components simultaneously

  ously. The binder system according to the invention is advantageously used for agglomerating combustible materials

  to form briquettes, balls, etc. When burning these briquettes, because of the use of molasses as a binder, the releases of sulfur-containing products in the form of gas are greatly reduced.

  Another advantage of the system according to the invention is that the ammonium salts used as a catalyst for molasses sublimate under the combustion conditions and give no ash. The agglomerates according to the invention have a good appearance and good crush resistance, even after

a long immersion in the water.

  According to an advantageous characteristic of the invention, the characteristics of the agglomerates can be further improved by treating them after cooking with a water-repellent product, in particular by soaking in a water-repellent bath. As the water-repellent product, paraffinic, vinyl, silicone, etc. derivatives may be used. Other advantages and characteristics of the invention will appear in the following examples. COMPARATIVE EXAMPLE 1 Crushed anthracite fines sieved at 4 mm are dried and mixed with 12% cane molasses and 3%

  The molasses has a solids content of between 60 and 80% by weight.

  100 g briquettes are prepared by pressing and baked for 30 minutes at 1,500 ° C. and then for 30 minutes at 2,400 ° C. The crush resistance measured after cooking on the Michaelis balance at the fiftieth is equal to

  kg, but after immersion for 16 hours in water, the crush resistance drops to less than 50 kg.

  COMPARATIVE EXAMPLE 2 The procedure is as in Example 1, except that

  as binder 12% molasses and 2% ferric oxide.

  After cooking, the briquettes obtained, of the same shape,

  have a crush strength equal to 180 kg.

  After 16 hours of immersion in water, this resistance drops to 120 kg.

EXAMPLE 1

  The procedure is as in Control Example 1, except that a binder system according to the invention is used at a rate of 6% of cane molasses,

6% ammonium lignosulfonate.

  An agglomerate of the same shape having a crush strength greater than 180 kg is obtained.

  After immersion in water for 16 hours, the loss of resistance is very low and less than 10%. EXAMPLE 235 The procedure is as in Example 1 except that 9% cane molasses is used,

4% ammonium lignosulfonate.

  The sinter has a mechanical crush strength greater than 165 kg The loss of characteristics after 16 hours of immersion in water is

less than 10%.

EXAMPLE 3

  The procedure is as in Example 1, except that 8% cane molasses, 4% ammonium lignosulphonate are used.

2% ammonium nitrate.

  An agglomerate having mechanical crush strength greater than 200 kg and a loss of characteristics of less than 10% after 16 hours immersion in water are obtained. EXAMPLE 4 The procedure is as in Example 1, except that 12% of cane molasses is used,

4% ammonium nitrate.

  An agglomerate having a crush strength greater than 185 kg and a loss of

  15 EXAMPLE 5 The procedure is as in Example 1, except that the cane molasses is replaced by beet molasses 12% of molasses are used. beet,

4% ammonium nitrate.

  The agglomerates obtained after firing have a crush strength greater than 190 kg and the loss of characteristics after a 16 hour immersion in water is only 15%. EXAMPLE 6

  The procedure is as in Example 1 except that

  mother of fine nickel ore with 12% molasses, and

4% ammonium nitrate.

  The agglomerates after cooking have a resistance

to the crushing of 180 kg.

  After 16 hours of immersion in the water, the resistance

at the crash fall to 150 kg.

Claims (9)

  1 Process for the manufacture of agglomerates by   pressure and heating, in particular at a temperature of between 100 and 3000 C approximately, of a mixture of fines, powders, granules, based on carbonaceous materials, in particular of fuels or based on ores, of a binder, optionally other additives, characterized in that the binder is a system comprising at least one molasses and at least one   molasses catalyst chosen from organic salts or inorganic ammonium.   Process according to Claim 1, characterized in that the molasses catalyst is chosen from at least one acetate, a carbonate, a chloride and a nitrate,   a sulfate, a phosphate, an ammonium lignosulfonate.   Process according to claim 2, characterized in that the molasses catalyst is selected from   ammonium lignosulfonate and ammonium nitrate.   4 Process for the manufacture of combustible agglomerates   compressing and heating a mixture of coal fines, powders or granules, anthracite, coke and a   binder characterized in that the binder is a com-   taking at least one molasses and at least one catalytic agent   molasses lyseur chosen from organic salts or inorganic ammonium.   Process according to one of claims 1 to 4,   in that the binder system is used   from 5 to 20% by weight of the agglomerate.   Process according to one of claims 1 to 5,   in that the agglomerates are subjected after cooking to a water repellent treatment.   7 Agglomerated products, in particular briquettes, balls,   obtained by implementing the method according to one of the   claims 1 to 6, characterized in that they comprise from 80 to 95% by weight of fines, powders, granules, based on carbon materials, in particular fuels, or other minerals and from 20 to 5% by weight of the system binder comprising at least one molasses and at least one organic salt or   inorganic ammonium as a catalyst for the weary.   Agglomerated products according to claim 7,   characterized in that they comprise 80 to 95% of   and from 20 to 5% by weight of a binder system comprising   at least one molasses and at least one molasses catalyst.   Agglomerated products according to claim 8,   characterized in that the binder system comprises from 40 to   % molasses and 60 to 10% ammonium lignosulfonate.   Agglomerated products according to claim 8,   characterized in that the binder system comprises from 0.5 to % by weight of ammonium nitrate.