DE1546642A1 - Binder and process for the production of agglomerates, in particular smokeless, water- and transport-resistant coal briquettes - Google Patents

Description

Binder and process for the production of agglomerates, in particular smokeless, water- and transport-resistant coal briquettes. The invention relates to a method for the production of a binder - for agglomerating powdery, granular or fibrous substances to - what . water and transport resistant materials, in particular from briquetting coal to smokeless, water and transport resistant fuel briquettes. Several binders are already known for forming fuel briquettes from briquetting coal. For this purpose, a binder is known ... consisting of a mixture of a curable synthetic resin and Pec, h ,. which is obtained by thickening cellulose waste liquor. It is also known to shape briquettes by treating the material to be agglomerated with water glass, then giving the mass the desired shape and the water glass with an acid, in particular acetic acid , is hydrolyzed, after which, if desired, a heat treatment can be applied.

It has now been found that, for the intended purpose, a geo-Ignetes Binder can be obtained by preparing a liquid mixture that a hardenable component, an aqueous alkali silicate solution, a water repellent and, if desired, a catalyst for curing the curable Component and optionally for hydrolysis of the alkali silicate.

A thermosetting plastic is preferably used as the hardenable component used.

The invention relates to a method for the production of agglomerates, especially of smokeless, water- and transport-resistant coal briquettes, whereby a fibrous .. powdery or granular substance to be agglomerated with the help of a Binder to the desired shape. is pressed, which process thereby it is indicated that the material to be agglomerated before or after its compression with one or more components of the detergent, as described above, is treated and the binding agent after any addition of the remaining component (s) during - or after the pressing - is hardened.

The binder is preferably cured thermally.

In the combustion-created haltenänBrennstoffbriketts with the inventive Verfahren- -er- '-ffeh --or ni-CHT r smoke malodorous Söheradeii than the Ailsgangsbrennstof f ällein -p-iitwickin would, during the briquettes during the - Ve'rb-r # ennu'n-g 'remain intact for an extremely long time. In addition, the briquettes have -a- -good- strength and # -Wäsäerbeständi-gkeit. - and to the extent that with normal Ti # ansportbedbedingungen61i #, # - even under particularly humid conditionsezi there is only insignificant breakage ei, - . # In addition - 'give . n the briquet ts. . when occurring Reibu - ng only -äusserst- infrequent St-aub and -; dirt 'aii.

Ej n --gL- »e # '- 1'gne-t-e'r- starting fuel provided irW generally from f eink rni-. g - e'm # Anihrd2 # it - 'oddr- -mkge'r-käfi-Iia --- c # the'Cem'ische-'-dävO'ti with other types of carbon h' * Examples of suitable hardenable components for the Binders according to the invention are: a) Phenoplasts, such as resorcinol resins, optionally modified with starch or dextrin, lignin phenol resins which contain lignin produced from sulphite liquor, cashew resin, essentially obtained from cardinol, tannin extract resins, essentially consisting of condensed tannins or Tanning extract resins modified with urea methanal resins; These phenol pl-aste are obtained by a condensation reaction with methanal, p-formaldehyde, furfural and / or glyoxal and can be thermally hardened, which can be accelerated with the help of catalysts such as aqueous ammonia solution or hexamethylenetetramine; b) urea resins, such as pure urea-formaldehyde resins or urea resins modified with cellulose, starch or dextrin; these resins are obtained by a condensation reaction with methanal - their thermal hardening below 150 ° C. can be accelerated with the help of acids such as oxalic acid or phosphoric acid or with aqueous ammonia solution or hexamethyl tetramine; e) Bi urethars, such as pure biuret formaldehyde resins or bi urethars modified with cellulose, starch or dextrin; these resins are obtained by a condensation reaction with methanal; d) thiourea resins, optionally modified with cellulose, starch or dextrin; e) melamine resins, such as pure melamine formaldehyde resins, or cellulose, starch or dextrin or alkyd resins modiflzierte Melaminharzej these resins are obtained by a Kändensationereaktion with methanal or other aldehyde "Your themtacht Hkrtuv4 unterL165 0 C, with the aid of acids werdeni beaohleunigt f) Furfurolharze, If necessary modified with Ligninj sulphiblue concentrates, urea, methanal or amines; their thermal hardening can be accelerated with the help of p-toluenesulphonic acid; g) all types of rubber latex, of which the butadiene-styrene copolymer latex is preferable due to its low price; they can be combined with a Use a coagulating agent, e.g. an ammonium salt, and a vulcanization catalyst, e.g. zinc diethyldithiocarbamate or benzothiazole; h) petroleum resins, including polymers of coumarone, indene and / or cyclopentadiene; their polymerization with the aid of organometallic catalysts, e.g. cobalt acetate .. in the presence of v on oxygen can be promoted; j) Hardening products made from protein substances, such as casein resins, optionally modified with water glass or soy protein, or soy flour resins, optionally modified with lignin or sulfite liquor concentrate; they are hardened with the aid of aldehydes, for example methanal, chromates or TI -,. nnin, and is accelerated by heating; k) Lignin hardening products such as lignin resins with phenol or triethanolamine, sulphite lignin or cellulose pitch; the hardening of which is essentially obtained by thermal analysis at temperatures up to 2800C.

The alkali silicate is preferably used in the form of a customary solution, for example soda waterglass of 40 b6. A urea-formaldehyde resin is preferably used as the hardenable component. The type of water repellent fabric is not critical. Paraffin in the form of an aqueous emulsion or silicones, for example, are suitable. The proportions of the binder are mixed with one another in a liquid state, so that the binder itself is also liquid and does not contain any solid parts that could separate out of the mixture under the influence of gravity. In this way, when the binder is mixed with the material to be agglomerated, a uniform distribution can be ensured.

The amounts of the main components of the binder are not critical. The optimal amounts can be determined by means of simple experiments for each purpose. In general, the liquid mixture contains 5 to 60 % by weight, "o" curable component (solid), 20 to 90 % by weight of alkali silicate (calculated as 40 ° B soda waterglass) and 20% by weight of the water-repellent substance. A suitable amount of a catalyst solution can be added to this mixture.

The optimum amount of binder to be mixed with the substance to be agglomerated depends on the type of substance to be agglomerated, the type of components of the binder and the desired properties of the agglomerates. For the production of fuel briquettes, 1 to 20% by weight of binder, based on the dry labeling carbon , can generally be used.

The binder can be as #, # i.) Hl nil Ü be wet when mixed with trockE.ner Br ikettierkohle, so that if wet coal does not need to be dried first.

The processing of the briquetting charcoal with the binding agent to briquettes can be done in different ways. The briquetting charcoal can be mixed with the Binu agent, pressed from the mixture of briquettes and heated to a temperature of 100 to 2000C during or after pressing. The briquettes can therefore be eaten hot (j. #. El) or first cold, pressed and then heated. It is also possible to first mix the briquetting charcoal with some components of the binding agent, after which briquettes are pressed from the mixture, which later end with the remaining component (s) of the binding agent, e.g. the water-repellent substance , before or after the thermal treatment. For understandable reasons, the catalyst is generally mean only in small quantities with a pre-sprayed binding agent medium to be mixed. In most cases it is advisable to bring the catalyst separately into contact with the dry briquetting charcoal before the binding agent is added before pressing, or with the mixture of briquetting charcoal and binding agent or with the finished briquettes pressed from briquetting charcoal and binding agent, immediately after pressing.

For fuel briquettes are good mechanical strengths and water resistance he wishes. These allow that on the briquettes, even if they are exposed to the weather how are exposed to rain, normal transport work can be carried out, without significant breakage occurring. Furthermore, they should behave well in the fire, Burn smokeless and stick together for a long time during the burning. It has found that these properties can only be found when using an s (-J1chen BI means that a combination of the three main components mentioned, namely curable component, an alkali silicate LLad a water-repellent substance contains. Through their mutual interaction it is achieved (1 that the finished product Above properties see - * - st.

Comparative tests showed that when using a binder, that contains two of the three main components mentioned, the r, -eiilins, -l, hte effect is not obtained.

Experiment I 180 g dry Brikettierkohle were washed with 20 cm 3 of a binder, obtained clLirch mixing .3 Vol.Tln. Soda water glass 40 0 B'e mixed with 1 part by volume of a urea methanal resin solution. The mass obtained was pressed to 40 ° C. in a screw press to form briquettes, which were heated to 1050 ° C. for 30 minutes.

The briquettes produced in this way proved themselves well in a fire. In an oven at a temperature of 750 OC, they ignited slowly and burned without developing smoke and without falling apart.

However, their water resistance was found to be insufficient. After immersion in water for 1 hour, they had absorbed 12.7 % by weight of water and could be broken very easily by hand.

Experiment IT 180 g of dry briquetting charcoal were mixed with 20 cm3 of a binder, obtained by mixing 5 parts by volume. Urea methanal resin solution with 1 part by volume paraffin emulsion. The mass obtained was pressed cold under a pressure of 310 kg / cm 2 to form briquettes, which were heated to 150 ° C. for 120 minutes.

These briquettes were exposed to a temperature of 8000C and fell apart after a few minutes. Smoke development was not noticed.

After being immersed in water for 20 hours, the briquettes had absorbed 6.2 % by weight of water and could be broken by hand.

Both their behavior in fire and their water resistance - proven therefore prove to be inadequate.

Experiment III 180 g of dry briquetting charcoal were mixed with 20 cm3 of a binder, obtained by mixing 14 vol. ', Parts. Soda water glass 40oBe ' mixed with 1 vol. Teaspoon paraffin emulsion. The mass obtained was pressed cold under a pressure of _310 kg / cm 2 to form briquettes, which were heated to 150 ° C. for 120 minutes. The behavior in fire of the briquettes obtained in this way was satisfactory. When burned in the oven at 800 ° C. , the briquettes remained intact and no smoke development was perceived.

However, when submerged in water, the briquettes fell after a few Hours apart by itself.

Experiment IV 180 g dry Brikettierkohle were. Tl. Paraffin emulsion is mixed with 20 cm 3 of a binder obtained by mixing 5 Val, Tln. Harnstoffmethanalharzlösung, sodium silicate 40oB # 14 vol. Tln. 1 and vol. The mass obtained was pressed cold under a pressure of _310 kg / cm 2 to form briquettes, which were heated to 150.degree. C. for 120 minutes.

The behavior in fire of the briquettes thus obtained was good. When burned in an oven at 8000C the briquettes remained intact and did not produce any smoke perceived.

The water resistance was also satisfactory. When submerged in After 24 hours, the briquettes had absorbed 4.1% by weight of water and theirs practically retained original mechanical strength, it is clear from these experiments to recognize that only when using a binder that is a combination of a curable component, an alkali silicate and a water-repellent substance contains, a fuel briquette with the desired properties can be obtained can.

Although the invention has been described in the foregoing essentially in regard to the production of fuel briquettes, it is - although the greatest advantages are gained in this application - not limited thereto. The binder obtained with the process according to the invention can, however, also be used advantageously in the production of other agglomerates, for example ore briquettes, building materials, such as building boards, floor coverings, insulation blocks and the like.

Example.-. 90 % by weight of briquetting coal with an ash content of q%, a gas content of 10 % and with the following sieve analysis: 0 -0.1 mm square mesh 6.9 wt 0.1-0.3 mm square mesh 9.5 % by weight 0.3-0.5 mm square mesh lo, 8 wt. -256 0.5-0.7 mm square mesh 15j5 % by weight 0.7-1.0 mm 0.uadratm ash 9.8 % by weight # 1 -2 -mm round holes 12.4% by weight 2 - _3 mm round holes ..13.7% by weight -3 - 4 mm . Round holes 16., 7 % by weight * > 4 mm round holes 4.7% by weight earth with 16 parts by weight. mixed with a binder. through-mixing: of 5 parts by volume of a homogeneous, liquid mixture of 35 % by weight of urea methanal resin (molar ratio of urea.

substance / methanal 3) and 65 % by weight of an aqueous 0.01% oxalic acid solution, with 14 vol. T1-n. Soda waterglass 400 3b (molar ratio Na, 0 -.- Si02 about 1 - 3, -35) and 1 volume, part 50 % by weight aqueous paraffin emulsion. which -have-been heated to 1050C-for 30 minutes6 The behavior of the briquettes thus-obtained in the fire-r was., - excellent; pie had good mechanical Strength and water resistance.

Claims (1)

P ate n tans p r U xhe 1.) Binder for the production of water- and transport-resistant agglomerates of powdery, granular or fibrous substances, characterized by a content of a hardenable component, an aqueous alkali silicate solution, a water-repellent substance and optionally a catalyst for hardening the curable component and / or for hydrolysis of the alkali silicate. 2.) Binder according to claim 1, characterized by a thermosetting plastic as the curable component. 3.) Binder according to claim 1 and 2, «characterized by a urea formaldehyde as the curable component. 4.) Process for the production of agglomerates, in particular smokeless, water- and transport-resistant coal briquettes, wherein a fibrous, powdery or granular substance to be agglomerated is pressed into the desired shape with the aid of a binder, characterized in that the substance to be agglomerated is pressed treated before or after pressing with one or more components of the binder according to claims 1 to and the binder, optionally after addition of the remaining component (s), hardens during or after pressing. 5.) The method according to claim 4, characterized in that the binder is cured thermally.