DE2606089C2 - Partially pyrolyzed particles of macroporous synthetic polymers and processes for their preparation - Google Patents

Description

2. Partial catfish pyrollated particles according to claim 1, characterized in that their surface is measured due to Ni adsorption, is between 50 and 1500 mVg, the macropores being 6 to 700 mVg, measured

by mercury adsorption, contribute to this surface.

3. Partial catfish pyrolled particles according to claim 1 or 2, characterized in that they are micropores of the size of the molecular sieves with average dimensions of 4 to 6 Å.

4. Partially pyrollated particles according to one of claims 1 to 3, characterized in that aab the Ratio of carbon to hydrogen between 2.0: 1 and 10: 1.

M 5. Partly pyrollated particles according to one of claims 1 to 4, characterized in that the The ratio of carbon to hydrogen of the particles is at least 9.0,

6. A process for the production of partially pyrolyzed particles according to claim 1 by thermal Decomposition of particles of synthetic polymers with ion exchange groups in an inert atmosphere with removal of the volatile constituents formed, characterized in that particles of a

macroretlcular ion exchange resin with pores with a mean diameter of 50-100,000 Ä In the inert atmosphere, which may contain an activating gas, thermally while maintaining the macroretlular structure decomposes, so that partially pyrolized porous particles with different pore sizes arise, whereby the larger pores from the macroretlular used as raw material Polymers originate and the smaller pores originate worldwide from thermal decomposition.

7. The method according to claim 6, characterized in that the thermal decomposition at a temperature takes place between 300 ° and 900 ° C.

8. The method according to claim 7, characterized in that the thermal decomposition at a temperature takes place between 400 ° and 800 ° C.

This invention relates to partially pyrolyzed polymer particles and a process for their preparation by thermal decomposition of particles of synthetic polymers with ion exchange groups. This partially pyro- *) Hslerten particles are suitable for removing impurities such as sulfur compounds, monomers and from other industrial impurities or from other contaminants from gases or liquids, such as B. for the removal of contaminants from liquid streams or wastes, for example Contain phenolic resins. The partially pyrolyzed particles are also useful for removing barblturates from blood suitable. They are particularly useful as adsorbents for removing vinyl chloride for cleaning of blood, for the recovery of phenolic compounds and, if the partially pyrolyzed particles Contain metals, also for use as catalysts.

Activated charcoal is the most commonly used adsorbent today. For the production of activated carbon for industrial customers For this purpose, a wide variety of carbonaceous raw materials are used, such as anthracite and bituminous coal, coke, charred husks and peat. The suitability of these materials depends on your low level Ash content from and from your availability in a uniform and unchanged quality *

The processes for activating the carbon can be divided into two categories. The first category includes what are known as "chemical activation processes" in which the carbonaceous material, or sometimes the charred material, is alkali-metal with one or more activating agents such as zinc chloride. carbonates, sulfates, biosulfates, sulfuric acid or phosphoric acid is impregnated and then pyrollslert or charred. The action of these materials appears to be based on dehydration with high yields of coal without the formation of tarry materials. The second category includes processes known as "heat treatment" in which the material to be charred or charred is heated to temperatures between 350 and 1000 ° C in the presence of CO ₂ , N ₁ , O ₁ , HCi, Cl ₁ , H ₁ O and other gases is heated. A part of the charring material burns in the surface area, and the "activity" of the coal is increased. By carefully monitoring the activation conditions, manufacturers are now able to produce activated carbons with large surfaces (800-200OmVg) in a wide range of uniform particle sizes.

The production of activated carbon by this process results in materials with the highest capacities for a wide range of adsorbates in both the liquid and the gaseous phase This material * · <Neighbors have the following drawbacks:

(a) Difficult and expensive thermal regeneration,

(b) high sprinkler losses of 10% per cycle,

(c) easy fracture of the particles of activated carbon and

(d) Insufficient controllability of the starting materials.

The object of the invention is to provide a material with improved properties for use as an adsorbent, to develop as molecular sieves and / or for catalysis, that is characterized by a high resistance against breakage and the formation of dust particles.

This object is achieved by partially pyrolyzed polymer particles, which are obtained by thermal decomposition of particles of synthetic polymers with ion exchange groups in an inert atmosphere with removal of the volatile constituents formed, and which are characterized in that a macroreticular ion exchange resin has been used as the synthetic polymer and the partially pyrollated particles contain at least 85% carbon, have an atomic ratio of carbon to hydrogen between 1.5: 1 and 20 : 1 , and a diverse pore distribution with macropores with an average dimension of 50 to 100,000 Å and micropores with an average dimension from 4 to 50 Å.

The invention also includes a process for making these partially pyrolyzed polymer particles. The partially pyrolyzed particles produced by pyrolysis in this invention are preferably spheres or pearls, which have considerable structural strength and cooperation. They don't break easily in two and do not form dust particles, as is the case with activated carbon. Because of the lack of risk of breakage The regeneration losses are often lower than with conventional activated carbon.

The pyrolysis of the macroretlular particles also allows better controllability of the starting materials and in / Ügedessen there are more uniform end products than those for the production of activated carbons used natural substances is possible.

In the invention, desired elements and desired functional groups can be used to increase the Adsorption of specific substances can easily be introduced into the new adsorbent material. The middle Pore size and the distribution of the pore size can be determined with well-defined synthetic starting materials reach well. These better control options allow the production of adsorbents for specific Adsorbates with adsorption capacities that are far greater than those of activated carbon.

In general, the starting polymer is controlled during pyrolysis. Temperatures for controlled Subject to tent rooms under certain environmental conditions. The primary goal of pyrolysis is thermal Decomposition, effectively removing the overnight products that have formed.

The thermal decomposition, which is also referred to as pyrolysis or heat treatment, is used in the Invention In r.-inar inert atmosphere carried out such. B. in an atmosphere of argon, neon, helium or nitrogen. The preferred starting material is a macroreticular ion exchange resin in bead form which the ion exchange group acts as a carbon-binding moiety that enables the polymer charred without merging, so that the macroreticular structure is retained and a high carbon yield is achieved. Examples of carbon-binding ion exchange groups are sulfonate, carboxyl, amine, sulfonic acids, carboxylic acid or qua'.ernare amine salt groups. These Groups are incorporated into a starting polymer by methods well known for the manufacture of ion exchange resins Methods introduced.

Suitable temperatures for the thermal decomposition are generally in the range -r.-jn 300 to about 900 ° C, although higher temperatures depending on the polymer to be treated and the desired Composition of the pyrolized finished product can be used. At temperatures above Around 700 ° C, extensive degradation of the polymer used as the starting material occurs, with pores being formed Form the size of molecular sieves in the product; H. Pores with a medium critical dimension from about 4 to 6 A. Such products constitute a preferred class of adsorbents in accordance with this invention. At lower temperatures, the pores formed by thermal decomposition usually have a mean critical size from about 6 to about 50 Å. A preferred temperature range for pyrolysis between about 400 and 800 ° C. As will be explained in detail later, the temperature control is essential to give a partially pyrollated product that has the desired composition, surface, Pore structure and the other desired physical properties. The duration of the thermal Treatment Is relatively negligible, provided there is a minimal duration of treatment at the increased Temperature takes place.

By controlling the conditions for thermal decomposition, in particular the temperature, the elemental composition and in particular the ratio of carbon to hydrogen (C / H) of the End product set in the desired catfish. By monitoring the thermal conditions, particles produce whose C / H ratio between that of the activated carbon and that of the known polymeric adsorbents.

The following table shows the effect of the maximum pyrolysis temperature on the C / H ratio of the End product when using macroretlular polymers with functional groups as starting material shown.

Table I. Source material]

maximum
Pyrolysis temperature

(1) Styrene / vinylbenzene copolymer adsorbent (Comparison)

(2) styrene / divinyibenzene copolymer, 400 ⁰ C ion exchange resin with sulfonic acid group (H * form)

(3) As (2) 500 ⁰ C

(4) As (2) 600 ⁰ C

(5) As (2) 800 ° C

(6) activated carbon

C / H ratio of the product

1.66

2.20 2.85 9.00

(Hydrogen negligible)

A wide range of pyrolyzed resins can be made. By looking at the porosity and / or the The chemical composition of the polymer used as the starting material varies, and so are those Conditions of thermal degradation or thermal decomposition changes. Generally the pyrolyzed ones cut Resins according to the invention have a ratio of carbon to hydrogen of 1.5: 1 to 20: 1, preferably 2.0: 1 to 10: 1, whereas activated carbon usually has a much higher C / H ratio, at least is greater than 30: 1 (see Carbon and Graphite Handbook, Charles L. Mantell, Intersclence Publishers, N. Y. 1968, p. 198). The product particles contain at least 85% by weight of carbon, the remainder being In the Mainly hydrogen, alkali metals, alkaline earth metals, nitrogen, oxygen, sulfur, chlorine and the like is, whereby these elements differ from the starting polymer or the ion exchange groups (carbon-binding Molecular proportions) derive. On the other hand, hydrogen, oxygen, sulfur, nitrogen, alkali metals, Transition metals, alkaline earth metals and other elements also derive from fillers, oils in the porous Polymers have been introduced to act as a catalyst and / or carbon-blinding molecular fractions serve or bring about some other effect.

The pore structure of the final product must have at least two distinct types of pores of different types medium size, d. H. there must be a multiform or multimodal pore distribution. The bigger ones Pores come from the macroporous resin used as the starting material, the macropores with a middle critical dimension between about 50 and about 100,000 Å. The smaller ones mentioned earlier Pores with a mean critical dimension of about 4 to about 50 Å originate from pyrolysis throughout the world and the maximum pyrolysis temperature. Such a diverse pore distribution is new and an important one Feature of the partially pyrolyzed particles produced by the process of the present invention.

The partially pyrolyzed particles according to the invention have a relatively large surface area due to the macroporous nature of the starting material and the smaller pores that form during pyrolysis. In general, the total _{surface area measured by N 2} adsorption is between about 50 and 1500 mVg. Contribute to this surface di ~, macropores Üblicherwelse about 6 to about 700 MVG, preferably 6 to 200 m ^J / g at and these values are determined by known methods by using mercury. The rest of the surface comes from the smaller pores from the thermal treatment. Be! the known thermal treatment of pore-free polymers, which belong to the so-called "gel type" (see DD Patent Schrlfter, 27 022 and 63 768) do not produce large pores, which are decisive for the adsorbents according to the invention. In addition, these thermally treated polymers do not have the effectiveness of the pyrolyzed particles of this invention. The following table explains the influence of macroporosity on the structure of the pyrolyzed products.

Table II Adsorbents made of sulfonated styrene / divinylbenzene copolymers-i *) with different macroporosities

55 sample no.

prior to pyrolysis polymer type

»DVB

mean pore size A

after pyrolysis
Surface surface

mVg niVg

1 non-porous 8th 0 0 3 / 2 macroporous 20th 300 45 338 3 macroporous 50 ~ 100 130 267 4th macroporous 80 50 570 570 5
6th macroporous 6th -20,000 6th 360

*) All copolymers were sulfonated to at least 90% of the theoretical maximum value
and were heated to 800 ° C in an inert atmosphere.

From the values in Table II it can be seen that the size of the surface area of the end product is not always depends directly on the porosity of the starting material. The surfaces of the macroporous starting polymers fluctuate by a factor of about 100, whereas the surfaces of the pyrollated resins only fluctuate by one Factor of about 2 differ. The non-porous gel type resin has a surface area well below the Starting materials for the invention, and results in a product with a surface area that is substantially below that of the pyrolled macroretlkuiären resins lies.

The duration of the pyrolysis depends on the time that is required to remove the volatile components from the special Polymers to remove and the heat transfer characteristics of the method used. In general the pyrolysis proceeds very quickly if the heat transfer is fast, e.g. B. In an oven with a flat Bed of material to be pyrollated or in a fluidized bed. About burning the polymer to be pyrollated To prevent this, the temperature of the polymer is usually not higher than 400 "C, preferred not higher than 300 ° C, before the pyrollated material is exposed to air. With the most preferred method, the material to be pyrollslerendc is heated very quickly to the maximum temperature, held at this maximum temperature for a short period of time (0-20 minutes) and then quickly up Cooled to room temperature before exposure to air. Products according to the invention can be identified by is manufacture this preferred method. By heating the starting materials to 800 ° C and then Im Cools over the course of 20-30 minutes. Longer residence tents at elevated temperatures are also useful, there no additional decomposition occurs if the temperature is not increased.

Aktivlerende gases such COj, NHY, _O:, HiO or mixtures thereof in small amounts tend to react with the polymer during the pyrolysis and thereby increase the surface area of the final product. Such gas additives can therefore optionally be used in the pyrolysis in order to give the adsorbents special characteristics.

The polymeric starting materials used in the invention for the production of the new adsorbents are ion exchange resins used, the macroretlkular homopolymers or copolymers of monoäthylenlsch or Polyäthylenlsch unsaturated monomers or condensable to macroporous polymers or copolymers Are monomers. These macromolecular compounds. Which in macroretlular form as starting materials are known. The preferred macro-secular ion exchange resins are conductive of polymers of ethylenically unsaturated aliphatic and aromatic compounds.

Examples of suitable monoethylenically unsaturated monomers which can be used for the preparation of the macroretlkuiären ion exchange resins are esters of acrylic acid and methacrylic acid, which ^{can contain an M of} the following radicals: ethyl, methyl, 2-chloroethyl, propyl, isobutyl, isopropyl, butyl, tert-butyl, sec-butyl, ethylhexyl, amyl, hexyl, octyl, decyl, dodecyl, cyclohexyl, isobornyl, benzyl, phenyl, alkylphenyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxyethyl, propoxymethyl, propoxypropyl, ethyloxybenzyl, hexoxybenzyl Hydroxyethyl and hydroxypropyl; furthermore ethylene, propylene, isobutylene, Dlisobutylen, styrene, Äthylvlnylbenzol, Vlnyltoluol, Vlnylbenzylchlorld, vinyl chloride, vinyl acetate, M vinylidene chloride, Dlcyclopentadlen, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, Dlacetonacrylamld, funktlonelle monomers such as Vlnylbenzolsulfonsäure, Vinylester, including vinyl acetate, vinyl propionate, Vlnylbutyrat , Vlnyllaurat, vinyl ketones, including Vlnylmethylketon, Vlnyläthylketon, Vlnyllsopropylketon, Vlnyl-n-butyl ketone, Vlnylhexylketon, Vinyloctylketon, methyl isopropenyl, Vlnylaldehyde, including acrolein, methacrolein, crotonaldehyde, vinyl ethers, including Vlnylmethyläther, Vlnyläthyläther, vinyl *> propyl ether, vinyl isobutyl ether, Vinylldenverblndungen, including vinylidene chloride bromide or bromochloride; also the corresponding neutral half-acid half-esters or free dibasic acids of unsaturated dicarboxylic acids, including itaconic, citraconic, aconl-, fumaric and maleic acid, substituted acrylamides, such as N-monoalkyl-, N, N-di-alkyl- and N-di-alkylaminoalkylacrylamide or Methacrylamide, where the alkyl groups can contain 1 to 18 carbon atoms, such as methyl, ethyl, isopropyl, butyl, hexyl, cyclo- ** hexyl, octyl, dodecyl, hexadecyl and octadecyl-aminoalkyl esters of acrylic acid or methacrylic acid, such as. B. / 5-Dlmelhylaminoäthyl, / J-Dläthylaminoäthyl or 6-Dimethylamlnohexylacrylate and methacrylate, alkylthloethyl methacrylate and acrylate, such as ethylthloethyl methacrylate, vinyl pyridines such as 2-VlnyIpyrlnln, 4-vinylpyrldine and 2-methyl.

In the case of the copolymers of ethylthioethyl methacrylate, the products can be oxidized to the corresponding Si Ί oxides or sulfones.

Polyäthylenlsch or polyunsaturated monomers, which are usually so during the polymerization behave as if they contained only one unsaturated group are isoprene, butadiene and chloroprene. Such monomers can be used in conjunction with the monoethylenically unsaturated monomers listed be used.

Examples of polyethylenically unsaturated compounds used for the production of the starting materials are: Dlvinylbenzol, Divlnylpyridin, Dlvnylnaphthallne, Diallylphthalat, Ethyleneglycoldiacrylat, Ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, divinyl sulfone, polyvinyl or Polyallyl ethers of glycol, glycerine, pentaerythritol, diethylene glycol, monothio or dhloderivatives of glycols and of resorcinol; Divinyl ketone, divinyl sulfide, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl succinate, "> Diallyl carbonate, diallyl malonate, diallyl oxalal, diallyladlpate, diallylsebacate, divinyl sebacate, diallyl tartrate, Dlallyl silicate, triallyl tricarballylate, triallylaconitate, triallyl cltrate, triallyl phosphate, Ν, Ν'-methylenedlacrylamide, N.N-methylenedimethacrylamide, Ν, Ν'-ethylene diacrylamide, trivinylbenzene, trivinylnaphthalenes and polyvinylanthracenes.

A preferred Kiasse of monomers of this type are äthyienlsch unsaturated aromatic compounds, # 5 = ß such as styrene, vinyl pyridine, Vlnylnaphthaiin, Vlnyltoluol, phenyl acrylate, vinylxylenes, and ethylvinylbenzene.

Examples of preferred polyethylenically unsaturated compounds are Divlnylpyridin, Dlvinylnaphtha-Hn, Divinylbenzene, trivinylbenzene, alkyldivinylbenzenes with 1 to 4 alkyl radicals with 1 to 2 carbon atoms,

substituted on the benzene nucleus, and alkyltrinylbenzenes having 1 to 3 alkyl radicals with 1 to 2 carbon atoms substituted on the benzene nucleus. In addition to the homopolymers and copolymers of these poly (vinyl) benzene monomers, one or more of them can be polymerized with up to 98% by weight. the entire monomer mixture with (1) monoethylenically unsaturated monomers or (2) other poly-, ethylenically unsaturated monomers than those defined above or (3) a mixture of (1) and (2). Examples of the alkyl-substituted di- and trylnylbenzenes are the various vinyltoluenes, di-methyl-ethylbenzene, 1 ^ -dlvinyl ^^. So-tetramethylbenzene, 1 ^, S-trylnyl ^ ao-trimethylbenzene, 1, - »- Dyl ,?> Trylnyl-3,5-d18thy! Benzene, 1,3,5-trylnyl-2-methylbenzene.
Most preferred are ion exchange resins based on copolymers of styrene, methylbenzene and

in ethylvinylbenzene.

Examples of suitable monomers capable of Konderiatlon are: (a) allphatlsche dibasic acids, such as maleic acid, fumaric acid, itaconic acid and 1,1-cyclobutanedic acid; (b) allphatlsche diamines, such as Plperazln, 2-Methylplperazln, Cls, Cls-Bls (4-aminocyclohexyl) methane, and Meta-xylylenedlamine; (c) glycols such as diethylene glycol, triethylene glycol, 1,2-butanedol and neopentyl glycol; (d) bischloro formats such as cis and trans-M-cyclohexyl chloroformate, 2,2,2,4-tetramethyl-1,3-cyclobutyl chloroformate and bischloro formats of other glycols; (e) hydroxy acids such as salicylic acid, m- and p-hydroxybenzoic acid and lactones such as propolactone, valerolactone and caprolactone; (0 diisocyanates, such as cis- and trans-cyclopropane-l ^ -dllsocyanat and cis- and trans-cyclobutane-l ^ -dllsocyanat; (g) aromatic divalent acids and their derivatives (such as ester anhydrides and SflurechloridfiV ι, B phthalic acid, phthalic anhydride, Terephthalic acid, isophthalic acid and dimethyl phthalate; (h) aromatic diamines such as benzldine, 4,4'-methylenediamine and Bls (4-aminophenyl) ether; (I) bisphenols such as bisphenol A, bisphenol C, bisphenol F, phenolphthaleln and resorcinol; 0 ) Blsphenolbls (chloroformate), such as Blsphenol-A-bls (chloroformate) and 4,4'-Dlhydroxybenzophenon-bls (chloroformate); (k) carbonyl and thiocarbonyl compounds, such as formaldehyde, acetaldehyde, thloacetone and acetone; (1) phenol and its derivatives, such as phenol and alkylphenols; (m) polyfunctional crosslinking agents, such as tri- or polybasic acids, such as trilamic acid, tri- or polyols, such as glycerine, tri- or polyamines, such as di-ethylene triamine and other monomers capable of condensation and mixtures of the aforementioned Mono meren.

The macroretlcular ion exchange resins used as starting materials in the invention can optionally an oxidizing agent or other reactive substance, such as sulfuric acid, or nitric acid

M containing acrylic acid, these substances at least partially making up the macropores of the ion exchange resins ai -fill. In addition, the ion exchange resins can also be filled with a filler such as carbon black, charcoal, Bone charcoal, sawdust or other carbonaceous materials are impregnated before pyrolysis. Such fillers are economical sources of carbon which can be used in amounts up to about 80% by weight of the ion exchange resins can be added.

The ion exchange resins used as starting materials can optionally also be a large number contained in dispersed metals in their atomic or ionic form. Such metals are for example Iron, copper, silver, nickel, manganese, palladium, cobalt, titanium, zircon, sodium, potassium, calcium, Zinc, cadmium, ruthenium, uranium and side earth metals such as lanthanum. It does not prepare anything for the specialist Difficulties in utilizing the ion exchange principle, the amount of metal and its shape to control.

Although the incorporation of the metals into the ion exchange resins is primarily to promote your Acting as catalysts, adsorbents can also contain metals that are useful. The into consideration Coming ion exchange resins, in acidic or basic form or in the form of metal salts, are Im Commercially available.

The partially pyrollated particles according to the invention can be used to separate a component of a Use the filling medium. Components from gaseous or liquid media can be touched with the pyrollslerten particles of the synthetic polymers are separated.

For example, with a pyrollslerten strongly acidic ion exchange resin based on styrene and Separate vinyl benzene vinyl chloride from air. During pyrolysis, the resin can in its hydrogen, iron

Hl, copper II, silver I or calcium form. You can z. B. the initial concentration of Vinyl chloride in air, preferably dry air, from 2 to 300,000 ppm to a level of less than 1 ppm

lower, with flow rates of 1 bed volume / hour to 600 bed volume / mln, preferably 10 to 200 bed volumes / mln usually works.

Compared to activated carbon, the adsorbents according to this invention have a number of advantages, such as

a lower heat of adsorption, a lower polymerization of the adsorbed monomers on the surface, a lower need for regeneration agent due to the diffusion kinetics, a lower loss of capacity after repeated cycles and a lower level of leakage prior to penetration. Similar effects are obtained in removing other impurities such as SO ₂ and HjS. These adsorbents are particularly useful for removing or reducing air pollution by removing contaminants such as sulfur-containing compounds, halogenated hydrocarbons, organic acids, aldehydes, alcohols, ketones, alkanes, amines, ammonia, acrylonitrile, aromatics, oil vapors, halogens, Solvents, monomers, organic decomposition products, hydrocyanic acid, carbon monoxide and mercury vapors.
Specific chlorinated hydrocarbons that can be removed with these adsorbents are:

2-chloro-4-ethylamine-6-isopropylamine-s-triazine
Polychlorocyclopentadlene isomers

Isomers of Benzolhexachlorld

60 * OctochloMJ-methane tetrahydrolndane l, l-Dlchlor-2,2-bls (p-ethylphenyl) ethane 1,1,1 -Trlchlor ^ -blsip-chloropheny-ethane

Chlorodolphenyldlchlorethylene I, I, -Blsip-chlorphenyD ^^ - trlchloräthanol

2,2-chlorovinyl methylphosphate

l ^ AIO.lO-Hexachlor-o ^ -epoxy-M ^ a.S.oJ-dlmethanolnaphthalln

1,2,3,4, fOJ

74% M.S.ö

1,2,3,4,5,6-hexachlorocyclohexane 2,2-Bls (p-methoxyphenyl) -l, l, l-trichloroethane chlorinated camphene with a chlorine content of 67-69%.

Other components that can be bound by these adsorbents from liquids are chlorinated Phenols, nitrophenols, surface active agents such as detergents, emulsifiers, dispersants and Wetting agents, hydrocarbons such as toluene and benzene, organic and inorganic waste dyes, color bodies from the manufacture of sugars, oils and fats, fragrance esters and monomers.

When the partially pyrollated polymer particles according to the invention are used as Ad-SOtbenUCü are exhausted, they can be regenerated. The most suitable regeneration agent depends on nature of the adsorbed material. In general, however, saline solutions, solvents, hot water, acids and steam are suitable. Thermal regeneration, which is also considered this adsorbent is a definite advantage.

The invention provides products with superior adsorption societies that do not require activation as they are otherwise required for numerous carbon-containing adsorbents. referred to as "activated carbon" will be required 1st. An advantage of the invention is that these adsorbents directly and In a stage can be obtained from said polymers by heat treatment. In some cases it can but activation with reactive gases can be advantageous in order to increase the adsorbing properties modify. As can be seen from the following Tables IU and IV, the adsorption properties substantially on the maximum temperature to which the resin used as the starting material is subjected, influenced. From Table III it can be seen that a temperature of 500 ° C gives an adsorbent, the optimal one Has properties for the removal of chloroform from water.

Resins treated at 800 ° C are able to adsorb molecules selectively according to their size (cf. Table IV). The resin treated at 800 ° C is also particularly effective in separating hexane and Carbon tetrachloride (see Table IV), since almost all of the carbon tetrachloride is on the surface of the Macropores rather than being adsorbed in the micropores. The seemingly superior selectivity of a commercial one Carbon molecular sieve (Example 5) is clearly due to the much smaller surface area of the macropores traced back. The resin treated at 500 ° C (No. 1 in Table IV) shows a lower selectivity for 2 molecules of different sizes, from which the importance of the influence of the maximum temperature during the Heat treatment reveals the adsorbent properties.

Table III Equilibrium of aqueous chloroform capacities for various adsorbents

All adsorbents are in equilibrium with 2 ppm CHClj In deionized
Water at room temperature

No.

sample

1 ·) S / DVB polymeric adsorbent

2 »Pittsburgh« granular activated carbon

3 sulfonated S / DVB resin pyrolls at 800 ° C

4 As 3, but activated with oxygen

5 As 3, but pyrolyzed at 500 ° C

*) S / DVB = copolymers of styrene and vinylbenzene

Equal weight capacity at 2 ppm

6.0 mg / g

dry. Adsorbent

10.2

Table IV Determination of the molecular separation through the uptake of equilibrium vapor

No.

sample

Sulphonated S / DVB pyrolls at 500 ° C As 1, but pyrolls at 800 "C Commercial activated carbon As 2, but treated with oxygen Carbon molecular sieve (commercially available)

. ') Effective minimum size 6.1 A') Effective minimum size 4.3 A

Capacity ("l / g) CCl ₄ ') hexane ³ )

12.1
3.4

41.0
17.6
0.50

15.6 15.7

40.9 22.7 12.1

The invention is explained in more detail in the following examples. example 1

A 40 g sample of a commercially available ion exchange resin based on a macroretlular copolymer From styrene and methylbenzene with sulfonic fluorine groups, In the Na * form (solids content 49.15%) became In a Filter tube arranged and washed with 200 ecm deionized water. 20 g FeClr-CHiO were approximately one liter of deionized water and dissolved through the resin sample arranged in a column headed for about 4 hours. Uniform and complete loading was determined visually. the The sample was then washed with one liter of deionized water, aspirated for 5 minutes and allowed to air Dried for 18 hours.

10 g of this sample, along with some other samples, was then pyrolled in an oven. The furnace had an argon gas supply of 7 liters per minute. The sample was heated to a temperature of 706 ° C. over the course of 6 hours, the temperature being increased by one step of about 110 ^° C. every hour. The sample was held at the maximum temperature for half an hour. The furnace was then heated and the furnace and its contents were allowed to cool while the argon gas continued to flow. In this pyrolysis, the adsorbent was obtained in a yield of 43% which were produced in the same way.

40 Tabel V composition fear weight Pyrolysis server ! Flattened 37 look sample before pyrolysis g travel mVg 390 weight 186 g / ccm on resin /) 10 example 1 222 0.67 45 A. Fe "' on resin B ', 10 example 540 0.62 B. Fe "' on resin A ¹ ) 10 example 299 0.82 C. on resin A ¹ ) 10 example - 1.07 D. \ on resin A ¹ ) 10 example 490 0.62 E. H on resin A ¹ ) 10 example _ 0.75 50 F. Ca " on resin C ¹ ) 10 example 0.89 G H on resin A ¹ ) 250 example - H H on resin A ¹ ) 675 example _ I. H In H ⁺ shape 521 example J Resin A ¹ ) on resin A ¹ ) 20th example 55 K H

') Resin A = macroreticulate ion exchange resin (basis: sulfonated styrene / divinylbenzene copolymer)

^! ) Resin B = gel-like ion exchange resin (basis: carboxyl-containing acrylic resin)

^J ) Resin C = gel-like ion exchange resin (based on sulfonated styrene / divinylbenzene copolymer) Example 2

The working procedure of Example 1 was modified in that 250 g of the same ion exchange resin, but in hydrogen form (obtained by treatment with hydrochloric acid), were pyrolled. The temperature was increased continuously to 760 ^° C. in the course of 6 hours. The sample obtained was cooled in 12 hours and had a surface area of 390 mVg.

Application examples
Adsorption of vinyl chloride

One sample was placed in a column made of stainless steel with an internal diameter of 1.69 cm. s The bed depth was 5.05 cm. Using a dilution device with a mixing chamber, a gas stream was generated containing 580 ppm vinyl chloride in air. This gas stream was passed over the column at a volumetric flow rate of 800 ml / min. The flow rate in the column was consequently 80 bed volumes / ratn. All experiments were carried out at room temperature and a pressure of 1.12 kg / cm ² abs. carried out. A flow of 10 ml / min was branched off from the outlet and passed into a detector with flame ionization for the continuous determination of vinyl chloride. Commercially available adsorbents from the applicant and a carbon activated with polymetaphosphate were tested in the same way. The results are given in the tables below.

Table VI ~ " is

Adsorption of vinyl chloride on sample K, H * form, pyrolyzed

Adsorption of vinyl chloride on sample B, Fe " ¹ " form, 40

pyrolyzed and with HjSO «, bed volumes - 20 ecm

time Leak mnmestans (min) (ppm VCM) Leakage in % 0 0 0 25th 0 0 50 0 0 75 0 0 100 0 0 125 0 0 150 0 0 166 1 0.1 200 34 5.8 225 242 42 250 454 78 275 569 98 300 580 100 Table VII

time Leak momentary (min) (ppm VCM) Leakage in% 0 0 0 25th 0 0 50 0 0 75 0 0 100 0 0 109 I. 0.2 125 284 49 150 521 90 175 568 98 200 580 100 Table VIII

Adsorption of vinyl chloride on sample C, Cu "" form, M

pyrolyzed

Tent leak momentary

(min) (ppm VCM) Leakage in %

65

0
0
0

0 0 25th 0 50 0

26 06 089 momentary continuation Impermeability in X time Leak 0 (min) (ppm VCM) 0 75 0 0 100 0 0.2 125 0 0.4 143 1 12th 150 2 42 175 68 69 200 244 86 225 401 97 250 501 100 275 564 300 580 Table IX

Adsorption of vinyl chloride on sample A, Fe " ¹ " form, pyrollslert

time Leak momentary (min) (ppm VCM) Leakage in % 0 0 0 25th 0 0 50 0 0 75 0 0 100 0 0 125 2.0 0.3 150 26th 4.5 175 112 19th 200 303 52 116 1 0.2

Table X

40 Adsorption of vinyl chloride on commercially available active

money

time Leak momentary (min) (ppm) Leakage in % 0 0 0 25th 0 0 50 0 0 75 0 0 100 0 0 115 0 0 117 1 0.2 200 580 100

Further application areas

Adsorption is carried out in a bed of 9.5 cm3 of Resin J using a stream of air containing 350 ppm vinyl chloride and with a flow rate of 160 bed volumes per «N minute is fed. The regeneration is followed by steam at 130 to 160 ° C for 20 minutes Air drying carried out for 10 minutes. This experiment is extended to over 15 cycles to show that a loss of capacity does not occur over several cycles. The results are from the following See Table XI.

10

Time·) 26 06 089 Weight Table XI capacity cycle 45 Volume 11.1 42 capacity 10.3 1 49 6.9 12.1 3 45 6.4 11.1 5 45 7.5 u, i 7th 37 6.9 9.0 9 40 6.9 9.8 11th 45 5.6 11.1 13th 6.1 15th 6.9

IO

*) Time in minutes up to an uncertainty of 1 ppm

The results of further comparative tests with commercially available resins or activated carbons are in the compiled in the following table.

J Table XII

30 35

(!) Trial with a feed concentration of 460 ppm be! ! 60 Bettvolümlna (BVVmIn) over a 10 cc sample

(II) Trial with a feed concentration of 350 ppm at 160 BV / mln over a 10 cc sample

(IH) Trial with a feed concentration of 1070 ppm at 160 BV / mln over a 10 cc sample

(IV) Test with a supply concentration of 860 ppm at 160 BV / mln over a 10 ccm sample

It should be noted here that sample H is a preferred embodiment of the invention acts according to example 2.

Compared to "US Product I", sample J shows a slight drop in capacity when the relative humidity is increased. This can be seen from the following information:

mg / cc

50

Adsorbent Volume Weight capacity capacity (mg / ccm) (mg / g) Sample D 14.4 13.5 Sample F. 9.8 f3, l Sample G 2.9 3.2 Activated carbon (US product I) 8.5 17.0 Activated carbon (Japanese product) 13.9 26.7 Pr: be H "»> 29.2 47.1 Sample H "» 26.6 42.4 Coal (US product Π) 7.6 16.8 Coal (US Produst IJP- 11.4 25.3

Volumka ^ azltat mg / cc rel. humidity "US Product I" Sample J 0 11.4 6.4 52 9.6 7.4 60 4.1 4.8 100 _ 2.3

Feed concentration - 850 to 1000 ppm Phenol adsorption w

20 ecm of sample I were given a feed concentration of 500 ppm phenol, dissolved in deionized water, subject. The flow rate was 4 BV / h. The sample showed less of a leak than 1 ppm at 38 BV. The capacity of the sample is calculated to be 25.0 mg / g with a leak of 3 ppm.

A commercially available macroretlcular adsorbent based on a styrene / divinylbenzene copolymer shows for Compare a capacity of 14.4 mg / g with a leak of 6 ppm.

Sample I is regenerated with methanol at a flow rate of 2 BV / h and it becomes 5 BV needed for a 71% regeneration.

Sample R was examined for its adsorption capacity for H ₂ S and SOj. The results indicated that significant amounts of both contaminants were adsorbed. Similar measurements showed only negligible adsorption of SO ₂ at 100 ° C.

Breaking strength

The physical integrity of the beads made from the pyrolyzed ion exchange resins is greater than that from other spherical adsorbents and granular activated carbons. This is shown in Table XIII. It is it is to be expected that the higher breaking strength will result in a longer service life compared to granular ones Coals that suffer a considerable loss of friction. The absence of dust is also made possible Applications for which activated carbon cannot be considered, e.g. B. to treat blood.

Table XIII

Breaking strength of pyrolyzed macroreticular polymers and other adsorbents

description

No.

Type

Breaking strength ') (kg)

sulf. S / DVB Copolymer, Heat Treated In Inerters Atmosphere at specified temperature

spherical activated carbon

granular activated carbon

1,400 ° C 2.3

2 500 ° C> 3.1 ² )

3 600 ° C> 3.4 ² )

4 800 ⁰ C> 3.4 ² )

5 1000 ⁰ C »3.6 ^} )

6 Japanese product 0.83

7 Japanese commodities 0.51 for trials

to treat blood

8 US product -0.90

') Mass, which must be placed on the upper of two parallel plates, around particles
to break between the plates (mean of at least 10 attempts).

² ) Lower limit at which at least one particle fails at the maximum load of 3.6 kg
was broken.

³ ) No particles were broken at the maximum load.

⁴ ) Since the particles were irregularly shaped, the experiment was interrupted as soon as one
Corner had broken off.

I) Carbon-binding molecules of the ion exchange resins

It has been found that a variety of molecular moieties have a carbon scavenging effect during the Have pyrolysis. A partial list of such molecular proportions and their effect is given in Table XIV. The exact chemical nature of the molecular antellar is not essential, as is any group or molecular antellar an ion exchange resin, which is a volatilization of carbon during pyrolysis impede. The exact chemical nature of the molecular antellar is not essential as any group or each Molecular shell of an ion exchange resin is suitable, which is a volatilization of the carbon during the Prevent pyrolysis, the ion exchange group immediately before the pyrolysis in situ in the macroreticular Resin can be fixed or bound.

Ii) Coal-absorbing agents brought in by soaking

By filling the pores of a macroreticular polymer with a reactive substance before the Pyrolysis can also prevent volatilization of the carbon in the polymers. In case of The use of sulfuric acid as an impregnating agent has shown that this effect is via sulfonation during the heating, through which a similar Materia! arises as it is used as a starting material In of sample 1 is listed in Table XIV. The greater carbon yield that is obtained from the impregnation Im Compared to the precaution received, is surprising and suggests that the impregnation other Carbon removal methods might be superior.

Ill) Impregnated Polymers

The impregnation is illustrated by Experiment No. 4 in Table XV. In this attempt, the Pores of a styrene / vinylbenzene copolymer containing carbon black are filled with HjSO * and pyrolled. the Carbon yield was higher than the corresponding experiment (sample 1) that in the absence of carbon black was carried out.

12th

Table XIV Carbon-binding molecular components Molecular Proportion

apparent yield carbon yield ') shape retention

S / DVB Sulfonate Carboxylate Fe ³ * 37.0 * 66% S / DVB Carboxylate Sulfonate Fe ³ * 47.3% 59% S / DVB Chloromethyl Gas phases chlorinated 34% 48% AN / DVB Nltrll quaternary amin salt 33% 73% S / DVB AmIn Ί Initial weight / final weight χ 100 according to 20.2% 30% 4-vinylpyrldln / DVB ¹ ) 21% 26% S / DVB 51% 59% S / DVB 51% 77% S / DVB 38.4% 76% S / DVB 24 % 46% warming to at least 600 ° C.

ruling ^J ) The molecular annulus is the nitrogen contained in the pyrldln.

Yes

Yes

Satisfactory

Yes

Satisfactory Satisfactory

Yes

Yes

Yes

Yes

Table XV Carbon binding through impregnating agents

attempt Copolymer Impregnating agent schelnb, - Kohler ^ toff- Shape- No. yield yield conservation I. S / DVB 98% HjSO ₄ 66.7 86% singled out 2 S / DVB Polyacrylic acid 42.4 91%) excellent Nl ² * shape 3 S / DVB AgNO, 32 41% singled out 4th S / DVB) soot *) 98% H ₂ SO ₄ _ 94% excellent

acid evaporates.
*) Impregnated with 20% by weight of carbon black during the polymerization.

ll "l._ l / _Ul _.... i ~ iT .. ~ · C / FVWD /""--— _A l ~ .... ^ - ■ - - _ ·. I.

Example 3 Sample No. 1 of Table XV was prepared by the following experiment.

A sample of 30.79 g of the macroretlular copolymer (20% DVB / S) was placed in a 30 mm OD quartz tube, which was suitable for the subsequent heat treatment. One end of the tube was plugged with quartz wool and the copolymer was placed over the quartz wool plug and the tube was oriented vertically. Isopropanol, deionized water and 98% H ₂ SO ₄ , 1 liter of each, were then passed through the resin over the course of 1.5 hours. Excess HjSO ₄ was in the course of further! Allowed 10 minutes to drain. About 5.5 grams of acid remained in the pores of the resin. The tube was then placed horizontally in a tube _{furnace through which N 2 was passed} at a rate of 4800 ecm per minute. During the heating process, a white smoke developed and then a reddish, pungent smelling oil. The end product was black, shiny, free-flowing beads which were approximately the same size as the resin used as the starting material.

Example 4 The following experiment made Sample 2 of Table XV:

A benzoic acid-containing copolymer was prepared in which a chloromethylated (20% DVB / S) with Saltpetre was oxidized. A batch of 20.21 g of the swollen in solvent and dried in vacuo Resin was placed in a quartz tube which was closed at one end with quartz wool. The pipe was placed horizontally in a heating mantle and gradually heated to 800 ° C over 200 minutes. The sample was then cooled to room temperature in about 120 minutes. While it was warming Nitrogen was passed through the tube at a rate of 4800 cem / min. A white developed Smoke while heating the sample. The end product consisted of shiny metailschwaizen vacations.

Typical multiple or multimodal pore distributions of the pyrolyzed polymer particles are based on the Table XVI below.

13th

Table XVI

Pore size distribution of macroretlular styrene / vinylbenzene copolymers
(unpyrollslert / pyrollslert and pyrollslert and treated) (ccm / g)

unpyrolled pore size area (A ¹

unpyrollslert

pyrollslert

800 * C

500 ° C

Oi treats 800 »C

H] SO ₄ soaked at 800 "C

4th 0 0.05 0 0 0.06 4- 6 0 0.12 0 0.09 0.09 6- 40 0 0 0.06 0.12 0.04 40-100 0.08 0 0.04 0.05 0 100-200 0.13 0.10 0.17 0.12 0.02 200-300 0.07 0.13 0.05 0.18 0.13 3 (XMOO 0 0 0.02 0.10 400-800 0 0 0.02 0 0.18 > 800 0 0 0 0 Example 5

Tap water (Spring House, Pennsylvania, USA) was mixed with about 1 ppm CHClj and with a Speed of 0.5 l / l per minute passed through 3 columns, the pyrollslerte particles of a sulfonated Containing styrene / vinylbenzene copolymers and were connected in parallel to a common point. Of the Waste was collected and the CHCb concentration was determined by gas phase chromatography. The results summarized in Table XVII show that the sample at 500 ° C. was used for comparison Adsorbentlen by far exceeds. To check the reproducibility of these results, a Second batch of a resin treated at 500 ° C tested under identical conditions, with even better Results were obtained. The best sample of the resin treated at 500 ° C can be about 14 times that of Bettvi Purify 'umina of the contaminated tap water than the granular activated carbon used for comparison. The different effectiveness of the two coals pyrolled at 500 ° C can be attributed to the much lower Oxygen content in the first-mentioned sample can be traced back. It is believed that less Oxygen leads to a hydrophobic surface, which creates the attraction for poorly soluble in water organic substances such as chloroform is enlarged. For the regeneration of these produced at 500 ° C Adsorbents, both steam and solvents, can be used with good success. These were loaded resin into small columns and treated with steam and with methanol. they received thereby the original equilibrium capacity. In a second series of tests, the Regeneration of the columns also carried out a treatment with 5 bed volumes of methanol. These results are also included in Table XVII. In the second series of experiments, the capacities of the pyrollslerten Resin (a) and polymeric adsorbent higher than the first cycle. It can be seen that the methanol in addition to complete regeneration has removed any impurities that were present at the beginning of the first cycle were present. The low capacity of the activated carbon after the second cycle shows one incomplete regeneration. The pyrollated material is slightly less easily regenerated than one commercial polymeric adsorbent material with about 1 additional bed volume of regenerant Is necessary to achieve the same degree of regeneration. Activated carbon, on the other hand, is much less easily regenerated than the adsorbents according to the invention with a regeneration of only 62% Treatment with 5 bed volumes (calculated from the ratio of the first to the second cycle capacity).

Table XVII Results of the experiments to remove chloroform from tap water I ppm CHCL] In tap water at 0.5 l / l at room temperature

BV at 10% Capacity up to 10% Leak Leak Cycle # 1 adsorbent pyrollated ion exchanger (500 ° C) (a) 6150 12.3 mg / g pyrollated ion exchanger (500 ° C) (b) 11850 24.9 Activated carbon 850 1.8 commercial polymer 630 2.2 Adsorbent Cycle No. 2 adsorbent pyrollated ion exchanger (500 ° C) (a) 8350 16.8 Activated carbon 525 1.3 commercial polymer 1175 4.0 Adsorbent

14th

Example 6

Table XVIII lists four different pyrollated resins which are typical of various types of production of the adsorbents according to the invention based on sulfonated styrene / vinylbenzene copolymers. Shown in your equilibrium capacities with phenol. These same resins were tested for loading and regeneration in columns and these results are also recorded in Table XVIH. An adsorbent treated with oxygen retains its column capacity within the existing error limits for all three cycles. Ute other samples appear to be only incompletely regenerated under the regeneration conditions used. The treatment with oxygen increases the »AnsatZK-Glelchgewlchtskapazltät« and the phenol capacity in the column only slightly, compared to the precursor which was not treated with oxygen. The regeneration capacity is _{improved exceptionally well by o} the oxygen treatment. The formation of pores in the range from 6 to 40 Å as a result of the oxygen treatment can be the cause of an increase in the diffusion rate within the particles and more effective regeneration.

Interestingly, the 500 ° C sample, which was excellent for removing chloroform, only had a low capacity for phenol. Since pores were present on the size of molecular sieves in the pyrollslerten at 800 ⁰ C sample, and absent in the pyrollslerten at 500 ° C sample. Is it likely that the smallest pores are the active sites for phenol adsorption?

Table XViii

Phenolic capacities of various adsorbents

Loading - 1500 ppm phenol In deionized water 4 BV / h flow rate at room temperature
Regeneration - 5 BV at 4 BV / hr flow

Description of the "approach" equilibrium cycle

capacity at 500 ppm (mg / g)

BV (ml) phenolic cap, at 1 ppm
Leak
g / lg / ccm

I. S / DVB
(sulfonated) Acid treatment
at 500 ° C 131 2. S / DVB
(sulfonated) (500 ° C) 121 3. S / DVB
(sulfonated) carbon black impregnated
H ₂ SOO ₄ 138 4th S / DVB
(sulfonated) H ₂ SO ₄ 96 5. Trade
product DVB polymer
Adsorbent 70 6th Trade
product grainy
Activated carbon

1 17.5 64 0.064 2 49 0.050 3 60 0.059 1 21.0 63 0.062 2 41 0.042 3 32 0.032 1 9.7 29 0.029 2 22nd 1 10.2 21 0.021 2 20th 0.019 1 J.032 7th 0.032 12th 0.032 1 0.105 7th 0.080 12th 0.070

Example 7

Pyrollated ion exchange resins were tested for their capacity to adsorb certain undesirable blood components to determine whether they could be used as artificial kidneys in hemodlalysis treatment. A wide variety of pyrollated sulfonated styrene / vinylbenzene polymers have been studied. From the results summarized in Table XIX, it can be seen that an oxygen-treated sample had a high capacity for adsorbing uric acid _t . The capacity for the uric acid adsorbent corresponds to the pore volume in the range from 6 to 40A which is created by the oxygen treatment (oxygen etching).

15th

Table XIX

»Use of equal capacities of pyrollated polymers for uric acid

5 equivalent at room temperature in aqueous phosphate buffer at pH 7.4

to 10 ppm

No. Description

treated with oxygen in 1st styrene / DVB

2. Pyrollslertes sulf. Styrene / DVB (800 ° C)

3. Pyrollslertes sulf. Styrene / DVB (800 ° C)

4. Pyrollslertes sulf. Styrene / DVB (1000 ° C)

5. Pyrollslertes sulf. Styrene / DVB (800 ° C) 6. Pyrollslertes sulf. Styrene / DVB (800 ⁰ C)

7. Pyrollslertes sulf. Styrene / DVB soaked with HjSO ₄ (800 ° C)

8. Pyrollslertes sulf. Styrene / DVB larger macropores) (800 ° C)

9. Pyrollslertes sulf. Styrene / DVB (500 ° C)

example

x There was determined the HarnsSureadsorptlon at various samples of pyrollslerten polymers derived from a sulfonated Styrcl / were derived all Dlvlnylbenzol copolymers. For this purpose, a 50 ppm uric acid in 0.1 N phosphate buffer at pH 7.4 was used. The uric acid solution was conveyed upward through a bed of 5 ecm of the polymer at a flow rate BV / h at a temperature of about 25 ° C. The results are summarized in Table XX.

Table XX

Uric acid adsorption from a buffer solution (50 ppm uric acid in the supplied solution)

Capacity b. IO ppm mg / g mg / g 18.4 mg / g mg / g mg / g 9.3 mg / g mg / g 9.0 8.3 mg / g mg / g 8.5 8.2 2.6 2.2 1.2

Leak Sample 1 Sample 1 Sample 2 Sample 3 Prcfoe 3 nacn: ppm ppm ppm 30 minutes 7.0 0.1 ö, ü 60 minutes lir 0.1 0.0 120 minutes 1 .. 0.3 0.5 180 minutes 22.2 0.9 2.0 240 minutes - 1.7 4.5 Sample 2 Pore distribution for the above samples: Pore diameter A:

4th 0.08 0.0 0.0.5 4- 6 0.12 0.09 0.04 6- 40 0.0 0.12 0.12 40-100 0.0 0.05 0.01 100-200 0.08 0.12 0.17 200-300 0.13 0.18 0.07 > 300 0.0 0.02 0.01

16

Claims (1)

Patent claims: 1. Partially pyrolyzed polymer plates, which are produced by the thermal decomposition of synthetic particles Polymer with ion exchange groups in an inert atmosphere with removal of the volatile gen components have been obtained, characterized in that the synthetic polymer used a macroreticular ion exchange resin and the partially pyrollsic particles (a) contain at least 85% carbon, (b) have an atomic ratio of carbon to hydrogen between 1.5: 1 and 20: 1, and ίο (c) a multiform pore distribution with macropores with an average dimension of 50 to 100,000 Å and Have micropores with an average dimension of 4 to 50 A.