JPS6351161B2 - - Google Patents

Description

[Detailed description of the invention]

The invention relates to partially pyrolyzed particles of resinous polymers, a method for their pyrolysis, their use in removing impurities such as sulfur compounds, monomers, and other industrial impurities or contaminants from gases; and applications for purifying contaminant-containing liquid streams such as phenols from waste streams and barbituates from blood. In particular, the present invention is suitable for partial pyrolysis as an adsorbent for vinyl chloride removal, blood purification, recovery of phenols, and as a catalytic agent for industrial and laboratory processes, especially when metals are added. The present invention relates to a reticular material (hereinafter referred to as "giant reticular material") having giant pores that communicate with each other and pass through the particles. The most commonly used adsorbent today is activated carbon. In the production of activated carbon for industrial purposes, anthracite and bituminous coals, coke, carbonized shells,
A wide variety of carbonaceous starting materials can be used, such as peat, etc. The suitability of such raw materials depends on their low ash content and availability in uniform and consistent quality. Activation methods can be considered in two categories. The first category includes zinc chloride, alkali carbonates, sulfates, carbonaceous materials or sometimes char.
Includes "chemical activation" methods of impregnation with one or more activating agents such as bisulfate, sulfuric acid or phosphoric acid and then pyrolysis (carbonization). The action of these materials is believed to be one of dehydration that provides a high yield of carbon without tarry substances. The second category includes carbides such as CO ₂ , N ₂ , O ₂ ,
350 ~ in the presence of HCl, _Cl2 , _H2O and other gases
It involves a method known as "heat treatment" which involves heating at a temperature of 1000°C. Some of the carbide is burned at the surface and the "activity" of the carbon increases. Through careful control of activation parameters, manufacturers are now able to produce high surface area products (80-2000 m ² /g) in a wide range of uniform particle sizes. The production of activated carbon by the above method provides a material with the highest effective carbon adsorption capacity for a wide variety of adsorbed substances in both liquid and gaseous phases.
However, these materials have the following drawbacks. (a) difficult and expensive thermal regeneration; (b) high regeneration losses of 10% per step; (c) brittleness of activated carbon particles; (d) lack of control over starting materials. Adsorbents produced according to the present invention via pyrolysis of synthetic organic polymers are preferably spheres with large structural integrity. They do not break down easily or produce dust particles as is the case with activated carbon.
Because of this lack of brittleness, regeneration losses are often lower than normal with activated carbon. Thermal decomposition of synthetic organic polymers also allows for a much greater degree of control over the starting materials, and thus the final product, than is possible with the naturally occurring raw materials used in the production of activated carbon. The introduction of desirable elements and functional groups to increase the adsorption capacity for a particular adsorbed substance is easily accomplished. Control of average pore size and pore size distribution is much more easily achieved with well-defined synthetic starting materials. This improved controllability has enabled the production of adsorbents with much greater adsorption capacity for specific adsorbed substances than is possible with activated carbon. The present invention provides partially pyrolyzed particles, preferably beads or spheres, produced by controlled decomposition of synthetic polymers with a specific initial porosity. In a preferred embodiment, the pyrolyzed particles are derived from the pyrolysis of a macroreticular ion exchange resin having a macroporous structure with macropores. Pyrolysis generally consists of subjecting the raw polymer to a controlled temperature for a controlled period of time under certain ambient conditions. The main purpose of pyrolysis is thermal degradation, which efficiently removes the volatile products generated. The maximum temperature ranges from about 300°C to about 900°C depending on the polymer to be treated and the desired composition of the final pyrolyzed particles.
Ranges up to ℃. At relatively high temperatures, e.g.
At 700°C and above, severe degradation of the polymer occurs with the formation of molecular sieve-sized pores in the product. Most preferably, pyrolysis (otherwise referred to as "heat treatment") is a carbon fixation moiety (otherwise referred to as "heat treatment") that converts the polymer into a carbide without melting it to preserve the macronetwork structure and provide high yields of carbon. -fixing
The method is carried out in an inert atmosphere consisting of, for example, argon, neon, helium, nitrogen, etc., using beads of macroreticular synthetic polymers substituted with moiety. Among suitable carbon fixation moieties are sulfonates, carboxyls, amines, halogens, oxygens (oxygens covalently bonded directly to the copolymer or to other atoms covalently bonded to the copolymer, such as carbonyl oxygens). , ester oxygen, etc.), sulfonate salts, carboxylate salts, and quaternary amine salts. These groups are introduced into the raw polymer by well known conventional techniques, such as the reactions used to functionalize polymers to make ion exchange resins. Carbon fixing moieties may also be produced by adsorbing their reactive precursors into macroreticular polymers and chemically bonding the carbon fixing moieties onto the polymer simultaneously or during heating. Examples of these latter reactive precursors include:
Includes sulfuric acid, oxidizing agents, nitric acid, Lewis acids, acrylic acids, etc. Temperatures suitable for carrying out the process of the invention include, although higher temperatures may be suitable, depending on the polymer to be treated and the desired composition of the final pyrolysis product.
Generally within the range of 300°C to about 900°C. Approximately 700℃
At temperatures above 500 Å, the raw polymer is severely degraded and forms molecular sieve-sized pores in the product, ie, with an average minimum pore size of about 4-6 Å, providing a preferred class of adsorbents in accordance with the present invention. At relatively low temperatures, thermally formed pores typically have an average effective pore size of about 6 Å to 50 Å.
The size range is about Å. The preferred range of pyrolysis temperature is about 400°C to 800°C. As described in more detail below, the desired product composition, surface area,
Temperature control is essential to obtain partially pyrolyzed materials with pore structure and other physical properties. The heat treatment time is relatively unimportant as long as the time of exposure to high temperatures is minimized. By controlling the conditions of pyrolysis, especially the temperature, the elemental composition of the final product particles, most importantly the carbon to hydrogen atomic ratio (C/H), is fixed at the desired composition. The controlled heat treatment provides particles with a C/H ratio composition between that of activated carbon and well-known polymeric adsorbents. The table below shows the effect of maximum pyrolysis temperature on the C/H ratio of the final product when using macroreticular functionalized polymers as starting materials.

Table: By varying the porosity and/or chemical composition of the starting polymer, and also by varying the conditions of pyrolysis, a wide range of pyrolytic resins can be produced. Generally, the pyrolytic resin of the present invention is 1.5:1 to
It has a carbon to hydrogen ratio of 20:1, preferably 2.0:1 to 10:1, whereas activated carbon usually has a C/H ratio that is higher, at least greater than 30:1 (Carbon and Graphite Handbook, Charles L. .
Mantell, Interscience Publishers, NY1968
, p. 198). The product particles contain at least 85% by weight of carbon, with the remainder mainly derived from the polymer or the functional groups (carbon fixing moieties) contained therein, hydrogen, alkali metals, alkaline earth metals, nitrogen, hydrogen, oxygen, sulfur, nitrogen, etc., introduced into the polymer pores [acting as a catalyst and/or carbon fixing moiety or having some other functional purpose] as a component of the filler; Alkali metals, transition metals, alkaline earth metals and other elements. The pore structure of the final product must contain at least two distinct sets of pores of different average pore sizes, ie, pores with a multi-peak pore distribution. Large pores preferably have an average minimum pore size of about
Resulting from a porous resinous starting material having macropores ranging from 50 to about 100,000 angstroms. The small pores generally range from about 4 to about 50 Å in diameter, depending largely on the maximum temperature during pyrolysis, as discussed above. Such a multi-peaked pore distribution is considered to be a novel and essential characteristic of the composition of the present invention. The pyrolytic polymers of the present invention have a relatively large surface area resulting from the macroporous porosity of the starting material and the smaller pores generated during pyrolysis. Generally, the total specific surface area as measured by _N2 adsorption ranges from about 50 to about 1500 ^m2 /g. Among these, giant pores were calculated using mercury adsorption technology,
Usually about 6 to about 700 m ² /g, preferably 6 to 200 m ² /g
g, and the rest is related to heat treatment.
Non-porous polymers, such as "gel" type resins, which have been subjected to heat treatment in the prior art (e.g. East German Patent No. 27022, February 12, 1964 and No. 63768,
(September 20, 1968) do not contribute to the macroporosity essential to the adsorbents of this invention, nor do they perform as efficiently as the pyrolytic polymers described herein. The table below shows the effect of macroporous porosity on product composition.

Table: The data in the table shows that the final surface area is not necessarily directly related to the porosity of the starting material.
If the initial surface area of the porous polymer with macropores is an index of approximately 100, then the heat-treated resin differs only by an index of about 2. The non-porous "gel" resin had a much lower surface area than the range of starting materials of the present invention and gave a product with a substantially lower surface area than the heat treated macroporous porous resin. The time of pyrolysis will vary depending on the time required to remove volatiles from the particular polymer and the heat transfer characteristics of the chosen process. Generally, this pyrolysis is very rapid when the heat transfer is rapid, such as in a furnace where shallow bed materials are pyrolysed, or in a fluidized bed.
To prevent combustion of the pyrolyzed polymer, the temperature of the polymer is usually reduced to below 400°C, preferably below 300°C, before the pyrolyzed material is exposed to air. The most preferred method of operation is to heat rapidly to maximum temperature and hold this maximum temperature for a short period of time (between 0 and 20 minutes).
holding and then rapidly reducing the temperature to room temperature before exposing the sample. The product according to the invention is heated to 800°C and heated to 20-30°C.
Produced by this preferred method of cooling for minutes. Holding the elevated temperature for a longer period of time may be equally satisfactory, since no further decomposition will occur unless the temperature is increased. Small amounts of activating gases such as CO ₂ , NH ₃ , O ₂ , H ₂ O or combinations thereof tend to react with the polymer during pyrolysis, thereby increasing the surface area of the final product. Such gases are optional and may be used to obtain special properties of the adsorbent. The starting material polymers used to produce the pyrolytic resins of the present invention include one or more monoethylenically or polyethylenically unsaturated monomers, or macroreticular polymers and copolymers reacted by condensation. Contains macroreticular homopolymers or copolymers of monomers that provide coalescence. The macroreticular resin used as a precursor in forming the macroreticular heat-treated polymer is not itself claimed as a novel composition. Any of the known materials of this type with suitable carbon fixing moieties are suitable. Preferred monomers are aliphatic and aromatic materials that are ethylenically unsaturated. Examples of suitable monoethylenically unsaturated monomers used to make particulate macroreticular resins include acrylic and methacrylic acids such as methyl, ethyl, 2
-Chloroethyl, propyl, isobutyl, isopropyl, butyl, tertiary-butyl, sec-butyl,
ethylhexyl, amyl, hexyl, octyl,
Decyl, dodecyl, cyclohexyl, isobornyl, benzyl, phenyl, alkylphenyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl, ethoxyphenyl, ethoxybenzyl, ethoxycyclohexyl, hydroxyethyl, hydroxypropyl Esters such as ethylene, propylene, isobutylene, diisobutylene, styrene, ethylvinylbenzene, vinyltoluene, vinylbenzyl chloride, vinyl chloride, vinyl acetate, vinylidene chloride, dicyclopentadiene, functional monomers such as vinylbenzene, sulfonic acid, Vinyl esters (including vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropyl ketone, vinyl n-butyl ketone, vinyl hexyl ketone, vinyl octyl ketone) , methyl isopropenyl ketone), vinyl aldehydes (including acrolein, methacrolein, and crotonaldehyde), vinyl ethers (including vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and vinyl isobutyl ether), vinylidene chloride bromide, or vinylidene compounds, including bromochloride, as well as the corresponding neutral or half-acid half-esters or free diacids of unsaturated dicarboxylic acids, including itaconic acid, citraconic acid, aconitic acid, fumaric acid, and maleic acid,
Substituted acrylamides such as N-monoalkyl, -N,N-dialkyl- and N-dialkylaminoalkyl-acrylamides or methacrylamides (alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, isopropyl, butyl, hexyl, cyclohexyl, octyl, dodecyl, hexadecyl and octadecyl), aminoalkyl esters of acrylic or methacrylic acid, such as β-dimethylaminoethyl, β-diethylaminoethyl or 6-dimethylaminohexyl, acrylates and methacrylates, alkylthioethyl- Methacrylates and acrylates such as ethylthioethyl methacrylate, vinylpyridines such as 2-vinylpyridine, 4-
Includes vinylpyridine, 2-methyl-5-vinylpyridine, and the like. In the case of copolymers containing ethylthioethyl methacrylate, the product can be oxidized to the corresponding sulfoxide or sulfone, if desired. Polyethylenically unsaturated monomers that normally behave as if they have only one ethylenically unsaturated group, such as isoprene, butadiene and chloroprene, may be used as part of the monoethylenically unsaturated category. Examples of polyethylenically unsaturated compounds include divinylbenzene, divinylpyridine, divinylnaphthalene, sialyl phthalate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, divinyl sulfone; glycol, glycerol, pentaerythritol, diethylene glycol, monothio or dithio derivatives of glycols,
and polyvinyl or polyallyl ethers of resorcinol; divinyl ketone, divinyl sulfide, allyl acrylate, diallyl maleate,
Diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sepacate, divinyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate, triallyl aconitate, triallyl citrate, triallyl phosphate,
N,N'-methylene diacrylamide, N,N'-
Included are methylene dimethacrylamide, N,N'-ethylene diacrylamide, trivinylbenzene, trivinylnaphthalene, and polyvinylanthracene. Preferred types of monomers of this type are styrene,
vinyl pyridine, vinyl naphthalene, vinyl toluene, phenyl acrylate, vinyl xylene,
It is an aromatic ethylenically unsaturated molecule such as ethylvinylbenzene. Examples of preferred polyethylenically unsaturated compounds include divinylpyridine, divinylnaphthalene, divinylbenzene, trivinylbenzene, alkyldivinylbenzenes having 1 to 4 alkyl groups of 1 to 2 carbon atoms substituted in the benzene nucleus,
and alkyltrivinylbenzenes having 1 to 3 alkyl groups having 1 to 2 carbon atoms substituted in the benzene nucleus. In addition to these homopolymers and copolymers of poly(vinyl)benzene monomers, 98% of one or more of these
up to (by weight of the total monomer mixture) (1) monoethylenically unsaturated monomers, or (2) polyethylenically unsaturated monomers other than the poly(vinyl)benzenes specified above, or (3) ), (1) and (2) may be copolymerized. Examples of such alkyl-substituted di- and tri-vinylbenzenes include various vinyltoluenes, divinyrenex, divinylethylbenzene, 1,
4-divinyl-2,3,5,6-tetramethylbenzene, 1,3,5-trivinyl-2,4,6-
trimethylbenzene, 1,4-divinyl-2,
3,6-triethylbenzene, 1,2,4-trivinyl-3,5-diethylbenzene, 1,3,5
-Trivinyl-2-methylbenzene. Most preferred are copolymers of styrene, divinylbenzene and ethylvinylbenzene. Examples of suitable condensation monomers are (a) aliphatic dibasic acids such as maleic acid, fumaric acid, itaconic acid, 1,1-cyclobutanedicarboxylic acid, etc., (b) piperazine, 2-methylpiperazine, Aliphatic diamines such as cis, cis-bis(4-aminocyclohexyl)methane, metaxylylenediamine, etc., (c)
Glycols such as diethylene glycol, triethylene glycol, 1,2-butanediol, neopentyl glycol, etc., (d) cis- and trans-1,4-cyclohexylbischloroformate, 2,2,2,4-tetramethyl- Bischloroformates such as 1,3-cyclobutylbischloroformate and the bischloroformates of other glycols mentioned above; (e) salicylic acid, m- and p-hydroxy-benzoic acid and derivatives thereof; (f) cis- and trans-cyclopropane-1,2-diisocyanate, cis- and trans-cyclobutane-1,2-diisocyanate, etc. Diisocyanates such as (g) phthalic acid,
Aromatic diacids and their derivatives (esters, anhydrides and acid chlorides) such as phthalic anhydride, terephthalic acid, isophthalic acid, dimethyl phthalate, etc., (h) benzidine, 4,4'-methylenediamine, bis(4) -Aromatic diamines such as -aminophenyl) ether, (i) bisphenol A,
Bisphenols such as bisphenol C, bisphenol F, phenolphthalene, resorcinol, (j) bisphenol A bis(chloroformate), 4,4'-dihydroxybenzophenone
Bisphenols such as bis(chloroformates), (k) carbonyl and thiocarbonyl compounds such as formaldehyde, acetaldehyde, thioacetone, acetone, etc., (1) phenols, alkylphenols, etc. phenols and derivatives, (m) polyfunctional acids such as tri- or polybasic acids such as trimellitic acid, tri- or polyols such as glycerol, tri- or polyamines such as diethylenetriamine, and other condensable monomers and mixtures of the above. Contains crosslinking agent. Ion exchange resins made from aromatic and/or aliphatic monomers provide a preferred type of starting polymer for making porous adsorbents. The ion exchange resin likewise contains functional groups selected from cations, anions, strong bases, weak bases, sulfonic acids, carboxylic acids, oxygen-containing halogens, and mixtures thereof. Additionally, such ion exchange resins may optionally contain oxidizing agents, reactive substances, sulfuric acid, nitric acid, acrylic acid, etc., at least partially filling the macropores of the polymer prior to heat treatment. The synthetic polymer may be impregnated with fillers such as carbon black, charcoal, bone char, sawdust or other carbonaceous materials prior to pyrolysis. Such fillers are an economic source of carbon and may be added in amounts up to about 90% by weight of the polymer. The starting polymer, when an ion exchange resin, optionally contains various metals in atomically dispersed form at ionic sites. These metals include iron,
Included are copper, silver, nickel, manganese, palladium, cobalt, titanium, zirconium, sodium, potassium, calcium, zinc, cadmium, ruthenium, uranium and rare earths such as lanthanum. By using this ion exchange mechanism, it is possible for one skilled in the art to control the amount of metal to be added as well as the distribution. Although the addition of metals to the resin primarily aids in its ability to act as a catalyst, useful adsorbents may contain metals as well. Synthetic polymers and ion exchange resins are commercially available in the form of acids, bases, or metal salts.
According to the invention, there is also provided an adsorption method for separating components from a gaseous or liquid medium, which comprises contacting the medium with pyrolyzed synthetic polymer particles. Strongly acidic exchange resins based on styrene-divinylbenzene, e.g. pyrolyzed from hydrogen, iron (), copper (), silver () or calcium () in the form of The initial concentration of vinyl chloride is 2 ppm at a flow rate of 1 bed per hour to 600 beds per minute, preferably 10-200 beds per minute.
It can be reduced from 300,000ppm to levels below 1ppm. Compared to activated carbon, the adsorbent of the present invention has a lower heat of adsorption, less polymerization of monomers adsorbed on the surface, requires less regenerant due to diffusion dynamics, and has improved performance when used repeatedly. It has advantages such as less decrease in adsorption capacity and less non-adsorption leakage before adsorption becomes impossible. Similar performance is seen when other impurities such as SO ₂ and H ₂ S are removed. The adsorbent of the present invention includes sulfur-containing molecules, halogenated hydrocarbons, organic acids, aldehydes, alcohols, ketones, alkanes, amines, ammonia, acrylonitrile, aromatics, oil vapor, halogens, solvents, monomers, It is particularly useful in the field of reducing air pollution by removing components such as organic decomposition products, hydrogen cyanide, carbon monoxide, and mercury vapor. Certain chlorinated hydrocarbons are 1,2,3,4,10 10-hexachloro-1,
4,4a,5,8,8 8a-hexahydro-1,
4 Endo-exo-5,8-dimethanonaphthalene 2-chloro-4-ethylamino-6-isopropylamino-s-triazine Polychlorobicyclopentadiene isomer Benzene hexachloride isomer 60% octochloro-4,7-methano Tetrahydroindane 1,1-dichloro-2,2-bis-(p-ethylphenyl)ethane 1,1,1-trichloro-2,2-bis(p-
chlorophenyl)ethane dichlorodiphenyl dichloroethylene 1,1-bis(p-chlorophenyl)-2,
2,2-trichloroethanol 2,2-dichlorovinyl dimethyl phosphate 1,2,3,4,10,10-hexachloro-6,
7-Epoxy-1,4,4a,5,6,7-dimethanonaphthalene1,2,3,4,10,10-hexachloro-6,
7-Epoxy-1, 4, 4a, 5, 6, 7, 8,
8a-octahydro-1,4-endo-endo-5,8-dimethanonaphthalene 74% 1,4,5,6,7,8 8a-heptachloro-3,2,4,7a-tetrahydro-4,
7-methanoindene 1,2,3,4,5,6-hexachlorocyclohexane 2,2-bis(p-methoxyphenyl)-1,
1,1-Trichloroethane Chlorinated camphene with 67-69% chlorine Other components adsorbed from liquids by the adsorbents of the present invention include chlorinated phenols, nitrophenols, surfactants such as detergents, emulsifiers, dispersants, etc. agents and wetting agents, hydrocarbons such as toluene and benzene,
Includes organic and inorganic dye waste, colorants from sugar, oils and fats, esters and monomers. When the adsorbent loses its adsorption capacity, it may be regenerated. The most suitable regenerants will vary depending on the nature of the material being adsorbed, but generally include salt water, solvents, hot water, acids and steam. Thermal regeneration of adsorbents has significant advantages. Adsorbent without Activation Superior adsorbents are produced by the present invention without the need for "activation" which is common with many carbonaceous adsorbents designated as "activated carbon". An adsorbent with superior and different properties over all other adsorbents is produced directly in one step by heat treating the polymer as described above. Activation with a reactive gas is sometimes a desirable optional method for improving adsorbent properties, but is not a necessary part of the invention. As shown in the table and table below, this adsorption is significantly affected by the maximum temperature to which the resin is exposed. As shown in Table 1, a temperature of 500°C provides an adsorbent that is optimal for removing chloroform from water. Resin heat-treated to 800°C can selectively absorb molecules depending on their diameter (see table).
This 800°C example is even more effective in selecting hexane over carbon tetrachloride, as almost all CCl ₄ is adsorbed on the surface of the macropores, as shown in the table. This is because it is not adsorbed by micropores. It is clear that the apparently superior selectivity of the commercial carbon molecular sieve (Example 5) is due to the very small surface area in the macropores. Resin heat-treated to 500℃ (No. in the table)
1) shows a much lower selectivity for molecules of two different sizes, clearly demonstrating the important influence of the maximum temperature during the heat treatment on the adsorption properties.

[Table] Same as No.3,

[Table] Same as No.3,
* S/DVB = copolymer of styrene and divinylbenzene

TABLE The following examples are illustrative but not limiting. Example 1 Amberlite 200 (registered trademark of Rohm and Haas for styrene/DVB sulfonic acid ion exchange resin) in Na ⁺ form (49.15% solids)
Put 40g sample of into the filter tube, and
Washed with 200 C.C. of DI (deionized) _H2O . 20g
of FeCl ₃ .6H ₂ O was dissolved in about 1 part of DIH ₂ O and passed through the columnar resin sample for 4 hours. Uniform and complete filling was observed with the naked eye. The samples were then washed with 1 part of DIH ₂ O, evacuated for 5 minutes and air dried for 18 hours. 10 g of this sample was then pyrolyzed together with several other samples in a furnace equipped with 7 argon gas inlets per minute. This sample was heated to 706℃ for 6 hours.
The temperature was raised to approximately 110°C per hour.
Samples were held at maximum temperature for 1/2 hour. Power to the furnace was turned off and the furnace and contents were gently cooled to room temperature with continuous argon flow over the next 16 hours. The yield of solid material was 43% after pyrolysis. The physical properties of this sample are listed in the table along with data for Samples B to G and similarly prepared I to K. Example 2 250 g of Amberlite 200 in hydrogen form (obtained by converting the sodium form with hydrochloric acid)
The method of Example 1 was modified in that the sample was pyrolyzed by continuously increasing the temperature to 760° C. over a period of 6 hours. The sample was then cooled for 12 hours, after which it exhibited a specific surface area of 390 m ² /g. Process Example Adsorption of Vinyl Chloride A 10 cm ³ sample is placed in a 1.69 cm internal diameter stainless steel column. The depth of the resin bed at that time is 5.05cm. By using a diluter with a mixer,
A gas stream containing 580 ppm vinyl chloride in air is generated and passed through the column at a volumetric flow rate of 800 ml/min. The column flow rate is therefore 1 min.
It is fast enough to pass 80 lines. All experiments were conducted at ambient temperature and at a pressure of 16 psig. A flow of 10 ml/min was separated from the effluent and fed continuously to a flame ionization detector for vinyl chloride analysis. Regular Rohm and Haas sorbent and Calgon activated carbon are similarly tested. The results are shown below.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

Table Alternative Process Example Adsorption was carried out by passing a vinyl chloride influent stream containing 350 ppm and having a flow rate of 160 columns per minute through a bed of resin J9.5c.c. . Regeneration is performed using steam at 130°-160°C for 20 minutes, followed by air drying for 10 minutes. Experiments were conducted for 15 cycles to demonstrate that there was no decrease in adsorption capacity over several cycles. The adsorption capacity is the value when the leakage reaches 1 ppm.

[Table] The results of comparative experiments with other commercially available resins and carbon are shown in the table below.

[Table] It should be noted that Sample H, prepared by the method of the Examples, is a preferred embodiment. When comparing sample J with PCB 12×30 carbon,
As the relative humidity increases, there is a slight decrease in adsorption capacity as shown below. Volume adsorption capacity mg/cc Relative humidity PCB 12 x 30 Sample J 0 11.4 6.4 52 9.6 7.4 60 4.1 4.8 100 - 2.3 Influent concentration - 850-1100 ppm Phenol absorption 20 c.c. of sample I was dissolved in DI water.
The influent was subjected to a concentration of 500 ppm. The flow rate is through four adsorption columns per hour. The sample is 38
Shows leakage of less than 1 ppm in column volume. The adsorption capacity of this sample was calculated to be 1.56 lbs/cubic foot, or 25.0 mg/g, at 3 ppm leakage. The commercial adsorbent Amberlite XAD-4 is used for comparison and exhibits an adsorption capacity of 0.9 lbs/cubic foot, or 14.4 mg/g, at 6 ppm leakage. If sample I is regenerated with methanol at a rate of 2 columns per hour, 5 columns will be required for 71% regeneration. Sample B was evaluated for its ability to adsorb H ₂ S and SO ₂ . The results show that significant amounts of both contaminants were adsorbed. Similar measurements on activated carbon showed negligible adsorption of SO ₂ at 100°C. Shatter Resistance The physical integrity of the pyrolytic polymer beads is greater than that of other spherical adsorbents and granular activated carbon as shown in the table. The superior resistance to fracture is expected to result in a much longer useful life compared to granular carbon, which has higher wear losses. Similarly, the reduced shedding of particulate matter by pyrolytic polymers allows them to be used in applications where activated carbon is not used, such as blood treatment.

[Table] (1) The particles are separated between the two plates until they become fragments.

[Table] Carbon fixation moieties It has been shown that an extremely wide variety of molecular moieties cause carbon fixation during pyrolysis. A partial list of those parts and the usefulness of each is shown in the table. The exact chemistry of this moiety is not important, as any group that helps prevent volatilization of carbon during pyrolysis is satisfactory for the process. Adsorbed Carbon Fixatives Filling the pores of macroreticular polymers with reactive substances prior to pyrolysis helps prevent volatilization of the carbon in the copolymer. In the case of sulfuric acid, this material shows that it undergoes a sulfonation reaction during heating, producing a material similar to the starting material of Sample 1 in the table. The greater carbon yield obtained by inhalation rather than pre-sulfonation was entirely unexpected, demonstrating the superiority of this method over other carbon fixation techniques. Impregnated Polymer No. 4 shows an example of impregnation in which the pores of a carbon black-containing S/DVB copolymer are filled with H ₂ SO ₄ and thermally decomposed. The carbon yield is higher than the corresponding experiment conducted without the presence of carbon black (Sample 1).

[Table]

【table】

[Table] Example 3 In the following experiment, sample No. 1 was manufactured. 30.79g giant reticular copolymer (20% DVB/S)
The sample was placed in a 30 mm outer diameter quartz tube suitable for subsequent heat treatment. One end of the tube was sealed with quartz hair and the copolymer was packed on top of the quartz hair to hold the tube vertically. Isopropanol, DI water, and 98% H ₂ SO ₄ (1 each) were passed sequentially through the resin for 1.5 hours. Excess H ₂ SO ₄ was poured off for 10 minutes. Approximately 5.5 g of acid remained in the pores of the resin.
Place this tube horizontally in a tube furnace and
N ₂ was passed through the tube at 4800 c.c./min. During heating white smoke and then a red, pungent odor oil came out of the sample. The final product was black, shiny, free-flowing beads approximately the same size as the starting resin. Example 4 In the following experiment, Sample 2 in Table 1 was manufactured. Benzoic acid copolymer with chloromethylated resin (20%
DVB/S) by nitric acid oxidation. 20.21 g of resin swollen with solvent and dried in vacuum,
One end was placed in a quartz tube filled with quartz hair.
The tube was held horizontally in a Glas-col heating mantle and gradually heated to 800°C over 200 minutes. The sample was cooled to room temperature within approximately 120 minutes.
Nitrogen was flowed through the tube at a rate of 4800 c.c./min during heating. White smoke came out from the sample during heating. The final product consisted of shiny metallic black beads. Example 5 A porous phenol-formaldehyde condensation polymer was thermally decomposed at 700°C by the procedure of the present invention. The carbon-fixing moiety is a hydroxyl group chemically bonded to an aromatic ring in the phenol-formaldehyde condensation polymer. This partially pyrolyzed polymer has a surface area (BET method) of 338 m ² /g.
and the pore capacity (mercury intrusion method) is 0.632,
The average diameter of the porous pores with macropores was 179 Å, the chemically bound oxygen content was 2.33% by weight, and the carbon to hydrogen atomic ratio was 9.5:1. This partially pyrolyzed phenol-formaldehyde condensation polymer sample was dried at 110° C. overnight and then exposed to saturated carbon tetrachloride vapor for 2 hours at room temperature. This sample adsorbed 31.9% of its dry weight of carbon tetrachloride, based on its original weight. This adsorbed sample was then heated to 70°C to regenerate. 92.6 of carbon tetrachloride adsorbed by this treatment
% removed. This sample showed an adsorbent with effective regeneration capacity for organic vapors.

Claims (1)

[Scope of Claims] 1. One or more ethylenically unsaturated monomers or monomers capable of condensation, or monomers thereof, to obtain a porous polymer having a carbon-fixing moiety. comprising the controlled pyrolysis product of a porous synthetic polymer derived from a mixture, the partially pyrolyzed particles comprising (a) at least 85% by weight carbon, (b) an average minimum pore size of about It shows a multi-mine pore distribution consisting of micropores in the range of 4 Å to about 50 Å and macropores in the range of about 50 Å to about 100,000 Å, (c) about 1.5:1
Partially pyrolyzed particles of a porous synthetic polymer having macropores characterized by having a carbon to hydrogen atomic ratio of ~20:1. 2. The partially pyrolyzed particles of item 1 above, wherein the particles are beads or spheres of about the same size as the ion exchange resin. 3 The specific surface area of the particles measured by N ₂ adsorption is in the range of about 50 to 1500 m ² /g, of which the macropores are in the range of about 6 to about
Partially pyrolyzed particles according to paragraph 1 above involving 700 m ² /g. 4. The partially pyrolyzed particles of claim 1, wherein the particles have micropores the size of molecular sieves with an average minimum pore size in the range of about 4 Å to 6 Å. 5. The partially pyrolyzed particles of paragraph 1 above, wherein the carbon to hydrogen atomic ratio is about 2.0:1 to 10:1. 6 Carbon fixed moiety is sulfonate, carboxyl, amine, halogen, oxygen, sulfonate salt,
Partially thermally decomposed particles according to item 1 above selected from carboxylate salts and quaternary amine salts. 7. The partially pyrolyzed particles of paragraph 1 above, wherein the particles have a carbon to hydrogen atomic ratio of at least 9.0. 8. At a temperature of about 300°C to about 900°C, under an inert gas atmosphere optionally containing an activated gas, one or more , ethylenically unsaturated monomers, or monomers capable of condensation, or mixtures thereof, to remove sufficient volatile components of the synthetic polymer. thermally decomposed for a sufficient period of time to produce (a) at least 85% by weight carbon, (b) micropores with an average minimum pore size in the range of about 4 Å to 50 Å and about 50 Å to about
(c) obtaining particles exhibiting a multi-peaked pore distribution consisting of macropores in the range of 100,000 Å and having a carbon to hydrogen atomic ratio of about 1.5:1 to about 20:1; and then subjecting the particles to the inert atmosphere. A method for producing partially pyrolyzed particles of a porous synthetic polymer having macropores, characterized in that the particles are cooled to a temperature lower than that at which oxidation occurs in air. 9. The method of item 8 above, wherein the pyrolysis is carried out at a temperature of about 400<0>C to 800<0>C.