CA1055179A - Refractory compositions - Google Patents

Abstract

Abstract of the Disclosure Solid refractory compositions comprising an inorganic particulate refractory material and a carbonaceous binder therefor comprising a substantially carbonized phenol-aldehyde condensate resin chemically modified by reaction with lignin and/or molasses. The refractory compo-sistion of the invention are characterized by an enhanced bending strength even at extreme elevated temperatures and a desirable diminished porosity compared to comparable refractory compositions having carbonaceous binders derived from conventional phenol-aldehyde resins.

Description

BACKGROUND OF THE INVENTION
The present invention relates to a refractory composition char-acterized by conta;ning as a carbonaceous binder for refractories a modified phenolic resin obtained by condensing phenol with lignin and/or molasses and/or an aldehyde in the presence of an acid catalyst or a basic catalyst. Tars and/or pitches have mainly been used as carbonaceous binders for refractories. However, these binders have some demerits. For example, hardening of the binder is extremely slow and development of strength during the temperature elevation stage is lO poor. A strength as high as possible at high temperature is required of refractories, so refractory products having even a slightly higher quality than quality conventional ones are always being sought after demanded. Recently, since carbonaceous binders conta1ning carcinogenic substances have posed a health problem, 1nvestigations of apply1ng 15 res1ns of h1gh carbonization rate such as phenolic resins and furan res1ns have been made. However, they have not as yet been successful.
In addition, the appllcat10n of general phenol1c resins, furan resins, 119nins or molasses independently as binders have also been studied, but an addit1ve 91v~ng a product with satisfactory refractory property 20 has not been found.
SUMMARY OF THE INVENTION
It has now been found that the carbonaceous binder of the present 1nvention 1s an excellent add1tive for carbonaceous refractories, since it is ~ore 1nexpensive and 1t has a far h1gher carbonizat10n rate and 25 strength after carbonization as compared with conventional tars and pitches and general phenol1c and furan res~ns. After intens1ve investi-gat~ons, the ~nventors have obta~ned a carbonaceous b1nder hav1ng the above-dsscribed merits by chemScal1y modifying a phenol1c resin w1th _ l ~

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i a lign;n and/or molasses which comprises heating said res1n with an extending agent selected from the group consisting of sulfite pulp lignin, kraft pulp lignin, molasses and mixtures thereof, the amount of lignin employed being about S to about 300 parts by weight per hundred parts by weight of the phenol and the amount of molasses employed being about 5 to about 500 parts by weight per hundred parts by weight of the phenol and the amount of refractory material employed being ~u~tably about 0,5 to about 1,000 part-~ by weight of the extending agent. A molded compo~ition i~
al o provided.
The process utilizing carbonaceous binders of the present invention in the production of a solid refractory composition comprises the steps of (1) forming a mixture of a particulate inorganic refractory material and an organic resin 1n the presence of a volat11e organic 11guid or water, where1n said refractory material 1s substantially 1nsoluble, 1n 15 an amount suffic1ent to prov1de a plast1c m1xture, said organic res1n comprising the condensate res~n of a phenol and an aldehyde chem1cally modif1ed by react1cn under heat~ng with an extend1ng agent selected from She group cons1sting of lign1n, molasses and mixtures thereof, the amount of 11gn1n employed be1ng about 5 to about 300 parts by 20 we19ht per hundred parts by weight of the phenol and the amount of molasses be1ng about 5 to about 500 parts by weight per hundred parts by weight of the phenol, (2) molding the resultant plast1c mixture to a des1red shape, (3) removing said liquid from said mixture by eva-porat10n to harden the resin and (4) calc1n1ng said mixture at an 25 elevated temperature under a non-ox1d1z1ng atmosphere to carbonize substant1ally a11 of sa1d resin and obta1n sa1d refractory compos1t10n DETAILED DESCRIPTIOH oF THE IN~EHTION
The carbonaceous b1nders accord1ng to the present 1nvent1cn are prepared by the ~o110w1ng techn1gues:

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(1) Novolak type phenolic resin modified with lignin (typically lignin containing sodium, potassium and/or calcium ions), and/or molasses is obtained by adding from about 5 to at most about 300 parts by weight of a lignin such as sulfite pulp lignin or kraft pulp lignin (hereinafter referred to as "a lignin") and/or from about 5 to at most about 500 parts by weight of molasses to 100 parts by weight of a phenol such as phenol per se, cresol or other alkyl-substituted phenol having 1 to 4 carbon atoms in the alkyl group (hereinafter such phenol reactants being referred to as "phenol"); then, adding thereto, if desired, at most 0.9 mole of an aldehyde such as formaldehyde, acetal-. dehyde, butylaldehyde or furfural (hereinafter referred to as "an aldehyde") per mole of said phenol; reacting the mixture together under - heating in the presence of an acid catalyst, for example, an organic acid such as common oxalic acid or p-toluenesulfonic acid, an inorganic acid such as hydrochloric acid or sulfuric acid or a "Lewis" acid such as aluminum chloride; and dehydrating the reaction product under atmos-pheric pressure or reduced pressure to obtain solid resin To this solid resin is added about 1-25 parts by weight of hexamethylenetetra-mine as hardening agent, if desired, and then the mixture is pulverized to a carbonaceous binder powder. The powdered carbonaceous binder may be dissolved further in an organic solvent to obtain a liquid car-bonaceous binder.

(2) A novolak type phenolic resin modified with lignin and/or molasses can also be obtained by reacting a phenol with an aldehyde in the presence of a common acid catalyst, then adding a lignin or molasses to the phenolic resin, reacting the mixture together in the presence or absence of a common acid catalyst under heat1ng; and dehydrat~ng the product under atmospheric pressure or reduced pressure. Hexamethylene-tetramine may be added to the product as a harden1ng agent, if desired,

- 3 -and pulverized to a powdered carbonaceous binder. The product may also be dissolved in an organic solvent to obtain a liquid carbon-aceous binder.
(3) A resolic phenolic resin modified with a lignin hnd/or molasses is obtained by adding from about 5 to at most about 300 parts by weight of a lignin andtor from about 5 to at most about 500 parts by weight of molasses to 100 parts by weight of a phenol, then adding thereto about 1-3 moles of an aldehyde per mole of said phenol, the mixture is reacted under heating in the presence of a common basic cata-lyst, for example, an inorganic base such as sodium hydroxide, potassiumhydroxide or barium hydroxide or an amine such as ammonia or triethyl-amine. The product is then dehydrated under reduced pressure to obtain syrupy carbonaceous binder. If necessary, this binder is diluted with an crganic solvent, typically using up to about 500 parts of solvent per 100 parts by weight of the binder resin. Conveniently, the amount of acid catalyst used is from about 0, preferably about 1, to about 10 parts per 100 parts by weight of the phenolic reactant and the amount of basic catalyst ~g'd is from about 1 to about 150 parts per 100 parts by weight of the phenolic reactant. In the preparation of a resolic phenolic resin modified with a lignin and/or molasses according to this invention, the lignin and/or molasses can be added at the beginning of the reaction. As for the refractory materials, inorganic materialssuch as silica, clay, alumina, carbon, magnesia and dolomite may be used.
The refractory compositions are made into refractories of definite shape or used as sealants of spouts or as 11nings of electric furnaces, blast furnaces, converters etc.
The aforementioned condensations ~1th 119n1n and/or molasses are carr1ed out 1n aqueous media, Genera11y about 1 to 1000 parts by we19ht of water per 100 parts by we19ht of the 11gn1n and/or molasses extender

- 4 -reactant are employed. Methods for applying the modi~ied phenolic resin of the present invention as a carbonaceous binder are illustrated below:
(1) Water or water which contains a small amount of a surfactant, an organic solvent such as a lower alcohol ("lower" meaning of 1 to 4 carbon atoms), a lower glycol such as ethylene glycol, diethylene glycol and propylene glycol, an oil or fat or a plasticizer such as tricresyl phosphate is added as wetting or plasticizing agent to the powdered resin, obtained by pulverizing a mixture of the novolak type phenolic resin modified with lignin and/or molasses and mixing hexamethylene-- tetramine, is mixed with refractory material and made into a clay-like mass. The resulting mixture can be directly used as a refractory material for indefinite shapes. If the mixture is molded with a press or the like and then dried or calcined under reduced pressure, refrac-tories in definite shapes are obtained.
(2) The same clay-like mass as above can be obtained by using a liquid resol type phenolic res~n (e.g. an aqueous part~ally reacted resol resin) modif~ed with a lignin and/or molasses as binder which, if desired, has been diluted with an organic solvent in the same manner as above.
(3) A c1ay-11ke mixture can be obtained by using (a) a liquid resol type phenolic resin modified with a lignin and/or molasses and (b) a powdered resin obtained by mixing novolac type phenol1c resin modified in the same manner and adding hexamethylenetetramine and pulverizing the m~xture (4) Refractories of definite shape are impregnated with novolac type pheno1ic resin mod~fted with a lignin and/or molasses without so1vent ~n mo1ten state, under heating or, ~f necessary, with a solvent at amb~ent temperature ~ 5 -105517g

(5) Refractories can be impregnated in the same manner with liquid resol type phenolic resin modified with a lignin and/or molasses which may be diluted with a compatible organic so1vent,

(6) Refractories can also be impregnated with a novolac type phenolic resin modified with a lignin and/or molasses similarly as described above, which has been dissolved in a compatible organic solvent.

(7) It is of course, possible to use the phenolic resins modified with a lignin and/or molasses together with tars, pitches or general phenolic resins and furan resins which have been used heretofore.
In the foregoing procedures advantageously from about 0 to about 500 parts by weight of water or aqueous organic solvent per 100 parts by weight of resin binder 1s employed to provide a moldable mass.
Generally the amount of refractory material used is about 0.5 to about 1,000 parts by weight per 100 parts by weight of the lignin or molasses reactant.
The present 1nvention wil1 be illustrated more concretely by means of examples, wh1ch do not lim1t the scope of the 1nvent10n. Parts and percentages in the examples are given by we1ght unless otherwise in-d1cated, ; EXAMPLE 1 Processes for the preparation of phenolic res1ns (A) through (I) mod1fied with a lignin and/or molasses (here1nafter referred to as "mod1f1ed phenol1c resins") used in Examples 2, 3 and 4 w111 be shown.
(1) 100 Parts of phenol, 100 parts of sulfite pulp lignin and 100 parts of molasses were reacted together in the presence of sulfuric ac1d catalyst at 100 0 for four hours. Thereafter, the react10n pro-duct was dehydrated under reduced pressure to obta1n a mod1f1ed phenol1c res1n of the novo1ac type w1th a melt1ng po1nt of 85 C. To 90 parts of the res1n thus obta1ned were added lO parts of hexamethylenetetram1ne 10~5179 and the mixture was pulverized into powder. Resin (A) was thus obtained.
(2) To a mixture of 50 parts of phenol, 50 parts of cresol and 200 parts of kraft pulp lignin, 37% aqueous formaldehyde solution was added in a quantity of 0.5 mole as formaldehyde per mole of phenol and cresol. The mixture was subjected to reaction in the presence of hydrochloric acid catalyst. The reaction product was dehydrated under reduced pressure to obtain novolac type modified phenolic resin having a melting point of 95 C. To 93 parts of the resin thus obtained were added 7 parts of hexamethylenetetramine and the entire material was pulverized into powder. Resin (B) was thus obtained.
(3) To a mixture of 100 parts of phenol, 50 parts of sulfite pulp lignin and 300 parts of molasses, 80% paraformaldehyde was added in a quantity of 1.0 mole as formaldehyde per mole of phenol. The mixture was subjected to reaction in the presence of sod1um hydroxide catalyst at 80 C for two hours. The reaction product was d0hydrated under reduced pressure to obtain a 11quid modified phenolic resin (C) of resol type having a viscos1ty of 20 po1ses at 25 C.
(4) To a m1xture of 80 parts of phenol, 20 parts of cresol and 150 parts of sulfite pulp lignin, 37% aqueous formaldehyde solution was added in a quantity of 2.2 moles as formaldehyde per mole of phenol and cresol. The m1xture was subjected to reaction in the presence of sodium hydroxide catalyst at 100 C for three hours. To the reaction mixture was further added 50 parts of sulfite pulp lignin, then de-hydrated under reduced pressure and diluted with methanol to obtain a 11qu1d modif1ed resol type phenolic res1n (D) having a viscosity of 10 po1ses at 25 C.
(5) To a m1xture of 100 parts of phenol and 150 parts of molasses, 80% paraformaldehyde was added 1n a quant1ty of 0,6 mole as formalde-hyde per mole of pheno1, The m1xture was sub~ected to react1On 1n the presence of oxa11c ac1d catalyst at 100 C for four hours. The react1On lOSS17~
product was dehydrated under reduced pressure to obtain a phenolic resin of novolac type having a melting point of 80 C. To gO parts of the resin were added 10 parts of hexamethylenetetramine and the mixture was pulverized Powdered resin (E) was thus obtained.
(6) To 100 parts of phenol, 37% aqueous formaldehyde solution was added in a quantity of 0 7 mole as formaldehyde per mole of phenol.
The mixture was subjected to reaction in the presence of oxalic acid : catalyst at 100 C for two hours. The reaction product was dehydrated under reduced pressure to obtain a novolac resin. Then, 50 parts of molasses and 150 parts of sulfite pulp lignin were added thereto and the mixture was stirred thoroughly. Aluminum chloride as catalyst was added to the mixture. The mixture was then dehydrated under atmospheric pressure. The entire material was dissolved in ethylene glycol. After cooling, 30 parts of hexamethylenetetramine were added thereto and the mixture was stirred thoroughly to obtain a 11qu1d mod1fied novolac type phenolic resin (F) having a v1scos1ty of 18 poises at 25 C, (7) To a mixture of 100 parts of phenol and 400 parts of molasses, 37% aqueous formaldehyde solution was added 1n a quantity of 0 9 mole as formaldehyde per mole of phenol The m1xture was subjected to reaction - 20 in the presence of tr1ethylam1ne catalyst at 80 C for three hours The reaction product was dehydrated under reduced pressure to obtain a modi-f1ed resol type phenolic resin (G) having a viscosity of 12 poises at

(8) To 100 parts of phenol, 37% aqueous formaldehyde solution was added in a quant1ty of 0 8 mole as formaldehyde per mole of phenol. The m1xture was sub~ected to react1an 1n the presence of a sulfuric acid catalyst to obta1n a novolac type phenol1c res1n precondensate. Then, 300 parts of kraft pu1p 11gnln were added thereto and the m1xture was st1rred thorough1y, The m1xture was then dehydrated under atmospher1c pressure to obta1n a mod1f1ed novo1ac type phenol1c res1n hav1ng a ~055~79 melting point of 109 C, To 88 parts of the resin were added 12 parts of hexamethylenetetramine and the resulting mixture was pulverized to obtain a powdered resin (H),

(9) To a mixture of 100 parts of phenol and 450 parts of sulfite pulp lignin, 37% aqueous formaldehyde solution was added in a quantity of 1,3 moles as formaldehyde per mole of phenol, The mixture was subjected to reaction in the presence of a potassium hydroxide catalyst at 100 C for one hour, The reaction product was dehydrated under re-duced pressure, Thereafter, the product was stirred thoroughly together with ethylene glycol to obtain a liquid modified resol type phenolic resin (I) having a viscosity of 55 poises at 25 C, Graphite as a refractory material was kneaded together with modi-fied phenolic resins (A) - (D) shown in Example 1 as binder in propor-tions shown in Table 1. Kneading temperature in the case of modified phenolic resins and general phenolic resins was at ambient temperature but in the case of pitches and tars was 80 C (under heating). The resulting clay-like mass was molded under a molding pressure of 300 Kg/cm2 to obtain preforms of a size of 15 m/m x 25 m/m x 120 m/m.
The preforms were heated slowly from room temperature to 1,200 C in coke breeze. The preforms were kept at l,200 C for fiYe hours and then cooled slowly to obtain carbonized moldings. Results of tests on physical properties of the products are shown in Table 1.

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1055~'79 Tests of the moldings were effected according to JIS R-2205 and JIS R-2213. The results shown in Table 1 suggest that when a ~inder of the present invention is used, apparent porosity after the car-bonization is smaller than in the comparative examples (conventional binders), i.e. moldings according to the present invention are more dense, and strengths thereof at ambient and high temperature are higher than the comparative ones by more than 30%.

Components in a proportion shown in Table 2 were kneaded together, magnesia clinker being used as a refractory material and modified phenolic resins (E-G) shown in Example 1 were used as binder. In case of using modified phenolic resin (E) (powder), a wetting agent (tricresyl phcs-phate) and the refractory material were first blended together and then resin (E) was added thereto and blending was continued at amb1ent temper-ature. In case of using modified phenolic res1n (F) or (G) (liqu1d),the res1n was kneaded simply together with the refractory material at ambient temperature. Also, 1n case of us1ng general phenal1c res1ns (11qu1d), the resin was kneaded s1mply together w1th the refractory material at ambient temperature. Also, in case of using general phenol1c res1ns (liguid), blending was effected at ambient temperature. In case of using a tar, blend1ng was effected under heating at 60~ C. The resul-t1ng clay-like mass was molded under a molding pressure of 500 Kg/cm2 to obta1n preforms of a size of 15 m/m x 25 m/m x 120 m/m. The preforms were dried at a temperature of 160 C for 10 hours. The product thus obtained must be classified as unfired refractories. The res1n wh1ch has been merely heated and thereby hardened acts as a bond and, if 1t 1s used actually at h19h temperature under a reduc1ng or non-ox1d1zing atmosphere, carbon bonds are formed there1n. For assess1ng the pract1cal propert1es of the moldSngs, the mold1ngs dr1ed 1n coke breeze were f1red at 4~0g C, 600 C and 1,909 C ~or three hours and the1r phys1cal propert1es were dete~nined, 1055~79 .~ ~ ~ ' o ~o ~ _ .

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The moldings were tested according to JIS R-2205 and JIS R-2213, The results shown in Table 2 indicate that the binders of the present invention impart a high strength to the moldings which have been dried and thereby hardened, and a higher strength at high temperature when employed for actual use as compared with those of conventional ~inders, Thus, the defect of conventional binders lacking strength, namely the carbon bonding power, at high temperature can be surmounted, Further, binders according to the present invention do not have serious defects accompanying conventional binders: low strength and slow hardening zt low and medium temperature range (400-600C). The binders according to the present invention have thus excellent properties desirable for binders of unfired refractories which properties have not been realized heretofore.

A clay-like mass (refractories of indefinite shape, for example, as ramming material or sealants) was obtained from carbon (coke powder) as refractory material and modified phenolic resin (H) or (I) shown in Example 1 as binder of the carbon by kneadlng them at ambient tempera-ture, The mixture was then pressed into lumps with a rammer to obtain , 20 preforms of a size of 50 m/m x 50 m/m, Physical properties of the , preforms were compared with those of conventional binders, Proportions -' of the components were as shown in Table 3, In case of modified phenolic resin (Hl, a wett~ng agent (polyethylene glycol) and the re-fractory material were first kneaded together and then resin (H) was added thereto and the kneading was continued, The results of the test are shown in Table 3, In the test, the resulting moldings were fired in coke breeze at temperatures of 250 C, 400 C, 600 C, and 1,000 C
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_ . . ___ _ Compress1ve 2 strength (Kg/cm ) . . . . . _ _ The above test was carried out according to JIS R-2206 The results shown in Table 3 show that the binders prepared according to the present invention have excellent properties which cannot be expected in conventional binders, namely the former binders have higher unfired strength (i.e. caking power) as compared with that of conven-tional binders and strengths thereof are high and uniform at tempera-tures ranging from low temperature (250C) to high temperature (1,000C).
In the use of the modified phenolic resins as a binder of refractories for indefinite shape as in this example, it is, of course, possible to obtain a proper working property (such as viscosity of the clay-like mass) by controlling the amount of the resin and wetting agent. Further, modified phenolic resins have produced more desirable results also as an impregnating agent as compared with conventional binders.

Claims (2)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

In a solid refractory composition comprising an inorganic refractory material and a substantially carbon-ized organic resin as carbonaceous binder therefor, the improvement wherein the resin comprises a condensate resin of a phenol and an aldehyde chemically modified by reaction under heating with an extending agent selected from the group consisting of sulfite pulp lignin, kraft pulp lignin, molasses and mixtures thereof, the amount of lignin employed being about 5 to about 300 parts by weight per hundred parts by weight of the phenol and the amount of molasses employed being about 5 to about 500 parts by weight per hundred parts by weight of the phenol and the amount of refractory material employed being about 0 5 to about

1,000 parts by weight of the extending agent.

The composition as claimed in Claim 1 wherein the phenol-aldehyde resin is a novolac resin.

The composition as claimed in Claim 2 wherein the extending agent is incorporated in the composition by reaction with the phenol, in the presence of a catalytic amount of an acid catalyst for said reaction, prior to condensation of the phenol with the aldehyde.

The composition as claimed in Claim 2 wherein the extending agent is incorporated in the composition by reaction with the phenol-aldehyde condensate in the presence of a catalytic amount of an acid catalyst for said reaction.

The composition as claimed in Claim 1 wherein the phenol-aldehyde condensate is a resol resin and the ex-tending agent is incorporated in the composition by reaction with the phenol in the presence of a catalytic amount of an acid catalyst for said reaction prior to condensation of the phenol with the aldehyde.

The composition as claimed in Claim 1 wherein the refractory material is selected from the group consisting of silica, clay, alumina, carbon, magnesia and dolomite, the aldehyde reactant is formaldehyde and the phenol reactant is selected from the group consisting of phenol and alkyl phenols having 1 to 4 carbon atoms in the alkyl substituent.

The composition of Claim 6 wherein the phenol reactant is phenol and the extending agent is molasses.

The composition of Claim 6 wherein the phenol re-actant is phenol and the extending agent is lignin from the group consisting of sulfite pulp lignin and kraft pulp lignin.

The process of producing a solid molded refractory composition comprising inorganic refractory material and a carbonaceous binder therefor which comprises the steps of 1) forming a mixture of a particulate inorganic re-fractory material and an organic resin in the presence of a volatile organic liquid or water, wherein said refractory material is substantially insoluble, in an amount sufficient to provide a plastic mixture, said organic resin comprising the condensate resin of a phenol and an aldehyde chemically modified by reaction under heating with an extending agent selected from the group consisting of lignin, molasses and mixtures thereof, the amount of lignin employed being about 5 to about 300 parts by weight per hundred parts by weight of the phenol and the amount of molasses being about 5 to about 500 parts by weight per hundred parts by weight of the phenol,

2) molding the resultant plastic mixture to a desired shape, 3) removing said liquid from said mixture by evaporation to harden the resin and 4) calcining said mixture at an elevated temperature under a non-oxidizing atmosphere to carbonize substantially all of said resin and obtain said refractory composition.

The process as claimed in Claim 9 wherein the solid molded refractory composition product is calcined at about 400° to about 1200° Centigrade to carbonize the resin.

A solid molded refractory composition impregnated with a condensate resin of a phenol and an aldehyde chemically modified with an extending agent selected from the group consisting of sulfite pulp lignin, kraft pulp lignin, molasses and mixtures thereof, the amount of lignin employed being about 5 to about 300 parts by weight per hundred parts by weight of the phenol and the amount of molasses employed being about 5 to about 500 parts by weight per hundred parts by weight of the phenol.

-18a-