Патент USA US2408616код для вставки
2,408,615 Patented Oct. 1, 1946 UNITED‘ 2408,6151" ‘ CATION’ EXCHANGE RESINS AND PRODUC- a‘ ‘ '- ~ ‘ ' TION THEREOFHQ James R.;Dudley,. Cos Cob, Conn”v assignor to American Cyanamid Company, New Yorka N. _Y., a. corporation of- .Maine ‘ "No Drawing. _ _ _ a v 7 Application March so, 1-944,v ] ' SerialaNo. 5283768 . , ». ' 2 ' ' 1 a ': V". ' ' absorption of cations fromwaterl equivalent to about 9,600 grains‘ of calcium carbonateperv cubic foot of resin. The density ofthe material'isabout This invention relates to cation active mate-j rials, that is, materials which exchange-'orex tract, by other means cations from fluid‘ media. An object of this‘ invention is to provide a sub 13.2 pounds per cubic ioot.‘ ' ' * > ' stantially water-insoluble resin having a relatively in Parts high capacity for the absorption of cations. This and other objects are attained by react ing furfural with mineral acidhalidesand resini< Sulfuryl chloride (4'.'0’m'ols)'__' ____________ __ 540 fyi'ng to a water-insoluble form. Furfural (10'.0>mo1s).__~_;__-_-___; _____ “1-. 1010 ‘ , ~ , r Glacial acetic acid_1______;_ _______ ,1 ______ “.840 " The following. examples arefgiven by. way of 10 ‘ As in Ex'ainpl'efl‘ ‘the sulfuryl chlorid‘e‘isr' dis illustration and not in limitation, The propor solved in'the acetic acid, this solution-is" cooled tions‘arei'n-parts byiweight, and the furfural is in an ice bath; and the’furfural‘ is‘ then, added 95% pure. ‘ slowly with stirring so that the ‘temperature of Example 1 v the solution does'notexceed 20°C. The solution 15 ' , ‘Parts is black- when the addition is complete and a Sulfuryl chloride (4.0 mols‘)l_»_‘__________ ____ __ 540 hard black brittle gel is formed on ‘standing over‘ Glacial acetic acid_.._'_, _____ __. _____ ..; ______ __ 840 night. Furfural ,(8‘.0 mols) ____ __ ________________ _. 808 The sulfuryl chloride is dissolved in the acetic acid, and the solution cooled'iin an i‘cebath. The furfural is thenfadded'slowly with stirring so‘that the temperature of the solution does ‘not exceed ' The gel is broken into small particles which are covered with water and allowed to stand over V20 night.‘ The Water is drained oiT and the resin driedffor 4.‘ vhours at- 100° C. - The ?nal Product has’ 'a, capacity for the‘ absorption of, cations iI'Om fwater equivalent-ttorabout 9,900vgrains of calcium . 20° C. When the addition is complete the solu¢ tion is black and uponzstanding overnight; a: very 25 carbonate‘per cubic footef resin and the :density soft black‘gel is formed. After'standing for-an of thel'materiallis- about 17‘.3=pounds per cubic foo-t. -» additional day the gel becomes ?rm and hard; " ‘ _ Example -5 . . The gel is reduced to particles of‘small size which are covered with water and allowed .to I The procedure of Example isiollowed except stand overnight. The water is then drained off ‘that instead of soaking the gel particles overnight and the resin dried for 4 hours at 100° v(3'; and they are suspended in water and the mixture is evaluated, The ?nal product exhibits a capacity boiled for 4 hours. The wate‘r’is'the'n ‘drained'off for the absorption or exchange of: cations from, and the resin driedforl 4 hours at 100° C. The water equivalent to about 8,000‘ grains‘ of calcium carbonate per cubic foot of resimand‘the" density of the material is‘ about 12.2" pounds per cubic foot.‘ '- ‘ ‘ 4 i7 ‘- ?nal product exhibits a‘capacity for the absorp ' 'tion ‘of‘ cations from waterjequivalent' to‘about 15,600 grains of ‘calcium carbonate per cubicifo’ot pf‘resin and th'e-Tdensitybf ‘the material is about 1 Example} l5lii'pbiunds per cubic foot‘; ’ Example: 1 is repeated but instead‘ oi. soaking the small-sized particles of the gel,‘ theyare. sus pended hours.» 7 40 . hours‘? at 145°‘ C.‘ to give aproduct having a capac . of ‘7.7 pounds. per cubic foot..--,.- * dot exhibitsja capacity for theabsorption or‘ ex change of cations from water, equivalent to about 45 1,100 .gr'ains ofcalcium. carbonate per‘ cubic, £00.11 ' ‘ of resin'and the d‘ensity'ofQthe materialisabout 105 pounds ‘per cubic foot; Eqcaymple, 6 The procedure of Example 4 is iollorvvedexcept that .instead, of soaking .the gel .particles i-c’v'er night, dry ‘steam is passed through the resin for 4 ‘hours as in‘ Example _'_3_. The resin is then dried 50 for 4 hours at 100° C; and the ?nal product found s '_ ‘Example 1 is repeated but' instead of soaking - , thegel particleslin- water overnight; dry 'steam'is to have a capacity Viorthe ‘absorption or exchange of cations from "water equivalent to about 14,100 “grainsof ‘calcium carbonate per cubic foot of resin. passed through theresin‘for 4 hours. ' After'this C. and the ?nal'product has?a capacitylmr vthe " 'carbonate'p'er cubic "footbf‘resin'. and a density The- water; is then drained off and the - resin dried for 4' hoursat 1.0090.‘ The ?nalrprodr ‘treatment the resin 'isvdried- for 4‘ hours at 100° ' "ity equivalent‘to,abouti12§900 grains‘of calcium in water and the mixture boiled ,for,4 ‘ Examples ~_ _‘ ’ " “ 'ft'er evaluation ‘the "resin is redrie‘d'fori 17 The ‘resin has a density of 16.0 pounds per cubic 65 foot. .-- we 2,408,615 3 4 Example 7 Example 12 . . , Parts Parts Sulfuryl chloride (4.0 mols) ______________ _. 540 Phosphorus oxychloride (0.5 mol) ________ __ Glacial acetic acid ______________________ __ 840 Glacial acetic acid ______________________ __ 105 Furfural (12.0 mols)‘ _____________ __y____'___ 1212 Furfural (1.0 mol) ____ “I _______ __._______ __ 77 101 The phosphorus oxychloride is dissolved in the acetic acid and the solution cooled to about 3° C. The furfural, cooled to about 5" C., is then added. The sulfuryl chloride is dissolved in the acetic acid, the resulting solution cooled in an ice :bath, and the furfural is then added slowly with stir ring so that the temperature of the solution does 10V The solution is black and after standing over night a soft brittle'rubbery black gel is formed. not exceed 20° C. Upon standing overnight a gel Upon warming up, an exothermic reaction oc is formed which is harder and more brittle than curs in which acetic acid and hydrochloric acid that of Example 4. ‘ ' I» fumes’ are distilled from the material. Upon The gel is broken into small-sized particles which are cured in an oven for 4 hours at 50° C. 15 ‘cooling a very hard brittle gel is obtained. Small -sized particles of the gel are covered and then for an additional 4 hours at ‘100° C._ with water and allowed to stand for 4 hours. The cured resin particles are then covered with Steamis then bubbled into the mixture for 4 water and allowed to stand overnight. The water hours, the water is drained o?, and the resin is is drained oiT and the resin dried for 4 hours at dried for 4 hours at 100° C. The ?nal product 100° C. 20 has a capacity for the absorption of cations from The ?nal cured and hydrolyzed product has a water equivalent to about 16,100 grains of cal capacity for the absorption or exchange of cations cium carbonate per cubic foot of resin and the from water equivalent to about 18,300 grains ‘of density of the material is about 17.5 pounds per calcium carbonate per cubic foot of resin and a cubic foot. _ density of 18.2 pounds per cubic foot. 25 Example '13 Ezcample 8 Parts Phosphorus oxychloride (0.5 mol) ________ __ 77 The procedure of Example 7- is repeated ex Glacial acetic acid ______________________ _- 105 cept that instead of soaking the cured resin par ticles overnight they are suspended in water and 30 Furfural (1.5 m0ls)_' ____________________ __ 152 The procedure of Example12 is followed boiled for 4 hours. Following this the water is throughout. The brittle black gel, somewhat drained off and the resin is dried for 4 hours at 100° C. The ?nal product exhibits a capacity. ?rmer than that formed in Example 12, has a capacity for the absorption of cations from water forthe absorption or exchange of cations from water equivalent to about 18,100 grains of cal 35 equivalent to about 17,300 grains of calcium car bonate per cubic foot of resin. The density of cium carbonate per cubic foot of resin and has a density of 18.4 pounds per cubic foot. the material is about 19.6 pounds per cubic foot. The mineral acid halides are preferably resin Example 9 i?ed with furfural alone although a minor por A hard brittle gel is prepared as described in 40 tion of the furfural may be replaced by other aldehydes, particularly formaldehyde, a polymer Example 7. Instead of curing small-sized par ticles of this gel by heating in an‘cven for a period of time, they are covered with‘water and allowed to stand overnight; ' The water is then drained off and the resin particles dried for 4 hours at 100° C. i of formaldehyde or a substance yielding form aldehyde. Other aldehydes which may be used include acetaldehyde, butyraldehyde, heptalde hyde, crotonaldehyde, acrolein, benzaldehyde, etc. The ?nal product has a capacity for the ab sorption or exchange of cations from water equiv The resins of the present invention may be cured by heating at a temperature ranging from alent to about 11,700 grains of calcium carbonate room temperature to about 150° C. for from sev 'eral hours to a day. The reactions of furfural with mineral acid ‘chlorides are necessarily carried out in anhydrous per cubic foot of resin and a density of 22.2 pounds per cubic foot. Example 10 Example 7 is repeated except that the curing step is omitted. The hard brittle gel particles are suspended in water and boiled for 4 hours. After draining off the water, the resin is dried for 4 hours at 100° C. and evaluated. The ?nal product has a capacity for the absorption of cations from water equivalent to about 10,800 grains of calcium carbonate per cubic foot and a density of 23.2 pounds per cubic foot. Example 11 Example 7 is repeated except that the gel is not cured but particles thereof instead are treated by solvents to prevent hydrolysis of the chlorides before sulfonation or phosphonation takes place. The reactions involved. in the preparation of these resins are undoubtedly complex. No at tempt has been made to determine the mecha nism andI do not wishto be ‘limited to any par ticular theory thereof. However, I believe that the rapidity, and in some cases the violence, of the reaction in its last stages may be explained in the following manner. Elimination of water in all probability takes place during the con .densation leading to the formation of a resin from furfural. The water thus liberated will re act with the acid chlorides (or the furfural acid chlorides) with the formation of a mineral acid passing dry steam therethrough for 4 hours as in and the liberation of heat. The acid thus formed Example 3, and the resin is then dried for 4 hours serves to accelerate further condensation and at 100° C. 70 the heat likewise has the e?ect of accelerating The ?nal product has a capacity for the ex thev reactions which are taking place. While the change of cations in water equivalent to about rate of reaction may be slow initially, these fac 12,800 grains of calcium carbonate per cubic foot, tors cause the speed of reaction to increase pro and the density of the material is about 21.7 gressively until theireaction becomes violent. pounds per cubic foot. 75 My new resinous materials may be used alone 2,408,615 I 5 or in admixture with other cation active mate rials. Furthermore, my resins may be applied before gelation to a suitable carrier such as diato maceous earth, clays, charcoal, etc. In this Way, the active resin is spread on the surface of a rela tively inert material and this enables one to employ a smaller quantity of resin than other wise to obtain the same active area. 6 other cations to the metallic state, as well as for many other reduction purposes. Obviously many variations in the processes and compositions described above may be made with out departing from the spirit and scope of the invention as de?ned in the appended claims. I claim: ' 1. A granular water-soluble composition of ‘ matter comprising the hydrolyzed product of re The granular resinous materials prepared ac action of a mixture including furfural and a min cording to my invention, and particularly those 10 eral acid halide selected from the group consist having a particle size less than 8 mesh, are useful ing of suliuryl chloride and phosphorus oxychlo in the removal of cations from ?uid media, espe cially aqueous solutions. The resins may be used in the hydrogen-activated form to remove cations from solutions of bases. My resinous cation active materials may also be employed as ex» ride and having a particle size of less than about ' 8 mesh. 2. A process which comprises condensing fur iural and a mineral acid halide selected from the group consisting of sulfuryl chloride and phos phorus oxychloride, gelling the resulting con densation product, heating the gel thus obtained with a sodium salt such as sodium chloride and 20 until it is insoluble in water, and hydrolyzing the change materials in accordance with the prin ciples applied to the use of the natural and syn thetic zeolites. Thus, the resin may be activated upon contact with a solution containing calcium, magnesium or other cations, an exchange of the latter ions for the sodium ions takes place. The activating solutions or regenerating solu tions are dilute acid solutions or dilute salt solu tions, e. g. about 0.2%—l0% of sulfuric acid, hy drochloric acid, sodium chloride, potassium chlo water-insolubilized gel. 3. A process which comprises condensing fur fural and a mineral acid halide selected from the group consisting of sulfuryl chloride and phos phorus oxychloride, gelling the resulting con densation product, hydrolyzing the gel thus ob tained, and heating the hydrolyzed gel until it is insoluble in water. ' ‘ . ride, etc. 4. A granular water-insoluble composition of To be sufficiently insoluble for practical use in the art of water puri?cation, a resin should have 30 matter suitable for the removal of cations from fluid media which comprises the hydrolyzed prod a sufficiently low solubility that it will not be dis uct of reaction of a mixture including furfural solution to be treated.‘ ' solved away rapidly by the and sulfuryl chloride, and having a particle size Thus, water should not dissolve more than about of less than about eight mesh. one part of resin in 1,000 parts of water when 5. A granular water-insoluble composition of passed through a bed of resin (after the ?rst cycle matter suitable for the removal of cations from comprising an activation, exhaustion and reacti fluid media whioh‘comprises the hydrolyzed prod vation of the resin) . uct of reaction of a mixture including furfural My resinous materials are useful for a wide and phosphorus oxychloride and having a particle Some of the uses which may variety of purposes. size of less than about eight mesh. 40 be mentioned by Way of example are: water puri 6. A process which comprises condensing fur~ ?cation; puri?cation of sugar juices; purification fural and a mineral acid halide selected from the of water from lead pipes; rem-oval of heavy metal . group consisting of sulfuryl chloride and phos ions from food, beverages and pharmaceutical phorus oxychloride, to produce a reaction prod products; decolorization of solutions containing coloring matters, etc. My condensation products 45 uct, gelling said product, hydrolyzing said prod uct, heating said product until insoluble in water may also be employed to recover valuable metal and granulating said product after gelation to a cations from dilute solutions, e. g., gold from sea particle size of less than about eight mesh. water, chromium from chrome tanning liquors, '7. A process which comprises condensing fur silver from photographic baths, etc. Another important application of my materials is in the 50 fural and phosphorus oxychloride, gelling the re sulting condensation product, hydrolyzing the gel absorption or adsorption of gases such as am thus obtained, heating the hydrolyzed gel until-it monia, amines, e. g., triethyl-amine, methyl amine, etc., from ?uid media either dissolved in a liquid or from vapors. _ is insoluble in water, and granulating said gel to a particle size less than about eight mesh where My furfural mineral acid halide condensation 55 by a product is obtained suitable for the removal of cations from fluid media. products may be used in reduction processes such as in reducing ferric ions to ferrous ions, mag _ nesium ions to a lower degree of oxidation and JAMES R. DUDLEY.