JPS6317485B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adsorbent material consisting of partially pyrolyzed particles of resinous polymers, a method for producing the same by pyrolysis, and impurities such as sulfur compounds,
Application of the above particles to remove monomers and other industrial contaminants or contaminants from gases, purify contaminant-containing liquid streams such as phenolics from waste streams, barbituates from blood. Concerning what to do. In particular, the present invention relates to partially pyrolyzed macroreticular materials as adsorbents for vinyl chloride removal, blood purification, phenolic recovery, and, especially when metals are incorporated, as catalysts in industrial and laboratory processes. The most commonly used adsorbent today is activated carbon. The industrial production of activated carbon uses a wide range of carbonaceous starting materials such as anthracite and bituminous coals, coke,
Use carbonized shells, peat, etc. The suitability of such materials depends on their low ash content and availability in uniform and consistent quality. Activation methods can be classified into two categories. The first category includes "chemical activation" methods,
In this case, the carbonaceous material or sometimes charcoal is treated with one or more activating agents, such as zinc chloride, alkali carbonates,
Impregnation with sulfate, bisulfate, sulfuric acid or phosphoric acid followed by pyrolysis (carbonization). The action of these substances appears to be one of dehydration, resulting in a high yield of carbon free of tarry substances. The second category is “heat treatment”
, in which charcoal is
Heated to 350-1000 °C in the presence of _CO2 , _N2 , _O2 , HCl, _Cl2 , _H2O and other gases. A portion of the charcoal burns, increasing the surface area and "activity" of the carbon. Careful control of activation parameters allows manufacturers today to produce high surface areas (800–2000 m ² /g).
Products can be produced in a wide range of uniform particle sizes. The production of activated carbon by the above method provides a material with maximum available carbon capacity for various types of adsorbates in liquid and gas phase. However, these materials have the following disadvantages: a thermal regeneration is difficult and expensive b high regeneration losses of 10% per pass c friability of activated carbon particles d lack of starting material control synthetic organic polymers The adsorbents produced in this invention by pyrolysis of are preferably spheres with large structural integrity. These adsorbents do not break apart or create dust as easily as activated carbon does. Because of this lack of friability, regeneration losses are often lower than normal with activated carbon. Pyrolysis of synthetic organic polymers also allows for much better control of the starting materials, and thus of the final product, than is the case with the natural combustion feedstocks used for activated carbon production. Incorporation of desired elements and functional groups to enhance the adsorption capacity for specific adsorbates is easily accomplished. Control of the average pore size and pore size distribution is much easier with well-defined synthetic starting materials. This improved control allows the production of adsorbents that have much greater adsorption capacity than activated carbon for specific adsorbates. The present invention provides partially pyrolyzed particles, preferably in the form of beads or spheres, produced by controlled decomposition of synthetic polymers with a specific initial porosity. In a preferred embodiment, the pyrolytic particles are produced by pyrolysis of macroreticular ion exchange resins having a macroporous structure. Generally, pyrolysis consists of subjecting the starting polymer to a controlled temperature under certain ambient conditions for a controlled time. The primary purpose of pyrolysis is to carry out the thermal decomposition while effectively removing the volatile products produced. Maximum temperatures range from about 300°C up to about 900°C, depending on the polymer being treated and the desired composition of the final pyrolyzed particles. Relatively high temperatures, e.g. around 700
C. and higher temperatures result in significant decomposition of the polymer and the formation of molecular sieve sized pores in the product. Most preferably, thermal decomposition (also referred to as pyrolysis or heat treatment) allows the polymer to be carbonized without melting, in order to preserve the macronetwork and provide high yields of carbon. Using beads of large network synthetic polymers substituted with carbon-fixing moieties, which are groups or chemical elements chemically bonded to the polymer, e.g. argon, neon, helium, nitrogen, etc. It is carried out in an inert atmosphere consisting of. Suitable carbon fixing components include sulfonates, carboxyls, amines, halogens, oxygen, sulfonates, carboxylates and quaternary amine salts. These groups are introduced into the starting polymer by well-known conventional techniques, such as reactions used for functionalizing polymers for the production of ion exchange resins. The carbon fixing component can also be provided by adsorbing reactive precursors into the pores of the macronetwork polymer, thereby chemically bonding the carbon fixing component to the polymer during heating. . Examples of these latter reactive precursors include sulfuric acid, oxidizing agents, nitric acid, Lewis acids, acrylic acid, and the like. Suitable temperatures for carrying out the process of the invention are generally from 300 to about 900°C, although higher temperatures may also be suitable depending on the desired composition of the polymer to be treated and the final pyrolysis product. be. At temperatures above about 700°C, the starting polymer decomposes strongly, resulting in the formation of pores in the product of molecular sieve size, i.e., an effective average pore size of about 4-6 Å, making it a preferred type of adsorbent according to the invention. is obtained. At lower temperatures, thermally generated pores typically have an effective average pore size ranging in size from about 6 Å to about 50 Å. The preferred range of pyrolysis temperature is about 400-800°C. the composition of the desired product, as explained in more detail below;
Temperature control is essential to obtain partially pyrolyzed materials with surface area, pore structure, and other physical characteristics. The time of the heat treatment is relatively unimportant, providing a minimal exposure time to elevated temperatures. By controlling the pyrolysis conditions, especially the temperature,
The elemental composition and most importantly the carbon to hydrogen atomic ratio (C/H) of the final product particles are fixed at the desired composition. The controlled heat treatment provides particles with a C/H ratio composition intermediate between activated carbon and known polymeric adsorbents. The table below illustrates the effect of maximum pyrolysis temperature on the C/H ratio of the final product using the macronetwork functionalized polymer as starting material.

[Table]
By varying the porosity and/or chemical composition of the starting polymer, and by varying the pyrolysis conditions, different types of pyrolytic resins can be produced. Generally, the pyrolytic resins of the present invention have a carbon to hydrogen ratio of 1.5:1 to 20:1, preferably 2.0:1 to 20:1.
10:1, while activated carbon usually has a much higher C/H ratio, at least 30:1 or higher (Carbon and Graphite Handbook).
Graphite Handbook), by Charles L. Mantell,
(See Interscience Publishers, NY1968, p.198). The product particles contain at least 85% by weight of carbon, with the remainder primarily hydrogen, alkali metals, alkaline earth metals, nitrogen, derived from the polymer or functional groups (carbon fixing components) contained on the polymer.
Hydrogen, oxygen, sulfur, chlorine, etc. and hydrogen, oxygen, sulfur, nitrogen, alkali metals introduced into the polymer pores as filler components (acting as catalysts and/or carbon fixing components or having some other functional purpose) , transition metals, alkaline earth metals and other elements. The pore structure of the final product is characterized by a multimodal distribution showing at least two sets of distinct pores with different average pore sizes, i.e. at least two peaks.
It must have pores that exhibit a certain distribution. The larger pores preferably result from a macroporous resin starting material containing macropores with a critical average pore size of about 50 to about 100,000 Å. The smaller pores generally have a pore size of about 4 to about 50 angstroms, depending primarily on the maximum temperature during pyrolysis, as discussed above. Such a multi-mine pore distribution is considered to be a new and essential feature of the composition of the present invention. The pyrolytic polymers of the present invention have a relatively large surface area due to the macroporosity of the starting materials and the smaller pores created during pyrolysis. Generally, the total specific surface area measured by N ₂ adsorption is about 50 to 1500 m ² /g. Among these, giant pores are usually about 6 to about 700 m ² /g, calculated using the mercury intrusion method.
Preferably, it occupies 6 to 200 m ² /g, and the rest is due to heat treatment. Void-free polymers, such as "gel" type resins, which have been subjected to heat treatment in the prior art [e.g.
20 days)] do not provide the requisite large porosity for the adsorbents of the present invention, nor do they exhibit the efficiency of the pyrolytic polymers described herein. The table below illustrates the effect of macroporosity on product composition:

Table: * All polymers were sulfonated to at least 90% of their theoretical maximum and heated to 800°C in an inert atmosphere.
From the table it can be seen that the final specific surface area is not necessarily directly related to the porosity of the starting material.
The starting specific surface area of macroporous polymers is approximately 100, whereas that of heat-treated resins is only about twice as large. The non-porous "gel" resin had a specific surface area well below the range of the starting materials of the present invention, yielding a product with a substantially smaller specific surface area than the heat treated macroporous resin. The time of pyrolysis depends on the time required to remove volatiles from the particular polymer and the heat transfer characteristics of the method selected. Generally, pyrolysis takes place very quickly when the heat transfer is rapid, for example in a furnace or fluidized bed pyrolyzing a shallow bed of material. To prevent combustion of the pyrolyzed polymer, the temperature of the polymer is usually lowered to below 400°C, preferably below 300°C, before the pyrolyzed material is exposed to air. The most preferred method of operation is rapid heating to the highest temperature, and a short period of time (0 to 20
minutes) and then rapidly cooling the temperature to room temperature before exposing the sample. The product according to the invention can be obtained by this preferred method at 800%
It was made by heating to ℃ and cooling for 20-30 minutes. Holding at elevated temperatures for longer periods of time is acceptable. This is because no additional decomposition occurs unless the temperature increases. A small amount of activated gas such as CO ₂ , NH ₃ , O ₂ ,
H ₂ O or a combination thereof tends to react with the polymer during pyrolysis, thereby increasing the specific surface area of the final material. Such gases are optional and can be used to obtain special properties of the adsorbent. Starting polymers that can be used to make the pyrolytic resins of the present invention include macromolecules consisting of one or more monoethylenically or polyethylenically unsaturated monomers that can be formed by condensation reactions to produce macronetwork polymers and copolymers. Included are network homopolymers or copolymers. The macronetwork resins used as precursors in the production of macronetwork heat-treated polymers are not themselves claimed as novel material compositions. Any of the already known materials of this type with a suitable carbon fixing component are suitable. Preferred monomers are aliphatic and aromatic materials that are ethylenically unsaturated. Examples of suitable monoethylenically unsaturated monomers that can be used in the preparation of granular macronetwork resins are: acrylic acid and methacrylic acid, such as methyl, ethyl, 2-chloroethyl, propyl, isobutyl, isopropyl, butyl, t-butyl, sec―
Butyl, ethylhexyl, amyl, hexyl, octyl, decyl, dodecyl, cyclohexyl, isobornyl, benzyl, phenyl, alkylphenyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl, ethoxyphenyl, ethoxybenzyl , esters such as ethoxycyclohexyl, hydroxyethyl, hydroxypropyl, ethylene, propylene, isobutylene, diisobutylene, styrene, ethylvinylbenzene,
Vinyl toluene, vinyl benzyl chloride, vinyl chloride, vinyl acetate, vinylidene chloride, dicyclopentadiene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, functional monomers such as vinylbenzene, sulfonic acid, vinyl acetate, vinyl propionate, Vinyl esters including vinyl butyrate and vinyl laurate, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropyl ketone, vinyl n-butyl ketone, vinyl hexyl ketone, vinyl octyl ketone, vinyl ketones including methyl isopropenyl ketone, acrolein, methacrolein, crotone vinyl aldehydes, including aldehydes, vinyl ethers including vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether, vinylidene compounds including vinylidene chloride bromide or bromo chloride, itaconic acid,
Corresponding neutral or half-acid half-esters or free diacids of unsaturated dicarboxylic acids including citraconic acid, aconitic acid, fumaric acid and maleic acid, substituted acrylamides such as N-monoalkyl, -N,
N-dialkyl-, and N-dialkylaminoalkylacrylamide or methacrylamide, where the alkyl group can have 1 to 18 carbons, such as methyl, ethyl, isopropyl, butyl, hexyl, cyclohexyl, octyl, dodecyl, hexadecyl and octadecyl), aminoalkyl esters of acrylic acid or methacrylic acid, such as β-dimethylaminoethyl, β-diethylaminoethyl or 6-
Dimethylaminohexyl acrylate and methacrylate, alkylthioethyl methacrylate and acrylate such as ethylthioethyl methacrylate, vinylpyridine such as 2-vinylpyridine, 4-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 which normally behave as if they had only one unsaturated group, such as isoprene, butadiene and chloroprene, can be used as part of the monoethylenically unsaturated class. Examples of polyethylenically unsaturated compounds are: divinylbenzene, divinylpyridine, divinylnaphthalene, diallyl phthalate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, divinyl sulfone, glycol, glycerol, pentaerythritol, diethylene glycol, glycol. , and polyvinyl or polyacrylic ethers of monothio- or dithio-derivatives of resorcinol, divinyl ketone, divinyl silifide, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate , diallyl adipate, diallyl sebacate, divinyl sebacate,
Diallyl tartrate, diallyl silicate, triallyl tricarballylate, triallyl aconitate, triallyl citrate, triallyl phosphate, N,N'-methylene diacrylamide, N,N'-methylene dimethacrylamide, N,
N'-ethylene diacrylamide, trivinylbenzene, trivinylnaphthalene and polyvinylanthracene. Preferred types of monomers of this type are aromatic ethylenically unsaturated molecules such as styrene, vinylpyridine, vinylnaphthalene, vinyltoluene, phenyl acrylate, vinylxylene, ethylvinylbenzene. Examples of preferred polyethylenically unsaturated compounds include divinylpyridine, divinylnaphthalene, divinylbenzene, trivinylbenzene, and an alkyl group having 1 to 2 carbon atoms substituted on the benzene nucleus.
-4 alkylvinylbenzenes, and alkyltrivinylbenzenes having 1 to 3 alkyl groups of 1 to 2 carbon atoms substituted on the benzene nucleus. In addition to homopolymers and copolymers of these poly(vinyl)benzene monomers, up to 98% (based on the weight of the total monomer mixture) of one or more of the following: (1) monoethylenically unsaturated monomers; (2) It can be copolymerized with polyethylenically unsaturated monomers other than the previously defined poly(vinyl)benzene, or (3) with mixtures of (1) and (2). Examples of alkyl-substituted di- and tri-vinyl-benzenes include various vinyltoluenes, 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-
These are 3,5-diethylbenzene and 1,3,5-trivinyl-2-methylbenzene. Most preferred are styrene, divinylbenzene and ethylvinylbenzene copolymers. Examples of suitable condensation monomers include: (a) aliphatic dibasic acids such as maleic acid, fumaric acid, itaconic acid,
1,1-cyclobutanedicarboxylic acid; (b) Aliphatic diamines such as piperazine, 2-methylpiperazine, cis,cis-bis(4-aminocyclohexyl)methane, metaxylylene diamine; (c) Glycols such as ethylene glycol, triethylene Glycol, 1,2-butanediol, neopentyl glycol; (d) Bischloroformates such as cis- and trans-1,4-cyclohexylbischloroformate, 2,2,2,4-tetramethyl-1,3- Cyclobutyl bischloroformate and other glycol bischloroformates mentioned above; (e) oxyacids such as salicylic acid, m
(f) Diisocyanates such as cis- and trans-cyclopropane-1,2-diisocyanate, cis- and trans-cyclobutane- 1,2-diisocyanates, etc.; (g) aromatic diacids and their derivatives (esters, anhydrides and acid chlorides) such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, dimethyl phthalate, etc.; (h) aromatic diamines For example, benzidine, 4,4'-methylenediamine,
Bis(4-aminophenyl) ether, etc.; (i) Bisphenols, such as bisphenol A, bisphenol C, bisphenol F, phenolphthalene, resorcinol, etc.; (j) Bisphenol bis(chloroformate), such as bisphenol A.
Bis(chloroformate), 4,4'-dihydroxybenzophenone bis(chloroformate); (k)
Carbonyl and thiocarbonyl compounds such as formaldehyde, acetaldehyde, thioacetone, acetone, etc.; (l) Phenols and derivatives such as phenols, alkylphenols, etc.; (m)
Multifunctional crosslinking agents such as tri- or polybasic acids such as trimentic acid, tri- or polyols such as glycerol, tri- or polyamines such as diethylenetriamine; and other condensation monomers and mixtures of the aforementioned compounds are included. Ion exchange resins made from aromatic and/or aliphatic monomers provide a preferred type of starting polymer for porous adsorbent production. Ion exchange resins can handle cations, anions, strong bases, weak bases,
It may also contain functional groups selected from sulfonic acids, carboxylic acids, oxygen-containing, halogens and mixtures thereof. Additionally, such ion exchange resins optionally contain oxidizing agents, reactive substances,
It may contain sulfuric acid, nitric acid, acrylic acid, etc. The synthetic polymers can be impregnated with fillers such as carbon black, charcoal, bone char, sawdust or other carbonaceous materials prior to pyrolysis. If the starting polymer is an ion exchange resin, it can optionally contain various metals in atomically dispersed form at ionic sites. As these metals,
iron, copper, silver, nickel, manganese, palladium,
cobalt, titanium, zirconium, sodium,
Potassium, calcium, zinc, cadmium, ruthenium, uranium and rare earths such as lanthanum may be mentioned. By utilizing an ion exchange mechanism, one skilled in the art can control the amount and distribution of metals to be incorporated. Although the incorporation of metals into the resin is primarily to aid in its ability to act as a catalytic agent, effective adsorbents may also contain metals. Synthetic polymeric ion exchange resins, whether in acid, base or metal salt form, are commercially available. According to the invention there is also provided an adsorption method for separating components from a gaseous or liquid medium, which consists in contacting the medium with particles of a pyrolyzed synthetic polymer. For example, hydrogen, iron (), copper (), silver ()
A strongly acidic exchange resin based on styrene-divinylbenzene, pyrolyzed from any form of calcium or calcium, can reduce the concentration of vinyl chloride in air, preferably dry air, based on the volume of one bed. 1 bed/hour to 600 beds/minute, preferably 10 to 200 beds/minute.
Initial concentration 2-300000 ppm at flow rate equivalent to bed/min
It has been found that the amount can be reduced from 1ppm to below 1ppm. Compared to activated carbon, the adsorbent of the present invention has less heat of adsorption, less polymerization of monomers adsorbed on the surface, requires less regenerant due to diffusion reaction rate, and has less capacity loss due to repeated action. Advantages include less leakage before adsorption reaches saturation. Similar performance was observed when removing other impurities such as SO ₂ and H ₂ S. The adsorbent of the present invention contains sulfur-containing molecules, halogenated hydrocarbons,
Organic acids, aldehydes, alcohols, ketones, alkanes, amines, ammonia, acrylonitrile,
It is particularly useful in the air decontamination field for removing components such as aromatics, oil vapors, halogens, solvents, monomers, organic decomposition products, hydrogen cyanide, carbon monoxide, and mercury vapor. Certain chlorinated hydrocarbons include: 1,2,3,4,10,10-hexachloro-1,
4,4a,5,8,8a-hexahydro-1,4endo-exo-5,8-dimethanonaphthalene 2-chloro-4-ethylamino-6-isopropylamino-s-triazine Polychlorobicyclopentadiene isomer Benzene Isomers of hexachloride 60% octochloro-4,7-methanotetrahydroindane 1,1-dichloro-2,2-bis-(p-ethylphenyl)ethane 1,1,1-trichloro-2,2-bis(p-
chlorophenyl)ethane dichlorodiphenyldichloroethylene 1,1-bis(p-chlorophenyl)-2,
2,2-trichloroethanol 2,2-dichlorovinyldimethylphosphate 1,2,3,4,10,10-hexachloro-6,
7-Epoxy-1,4,4a,5,6,7-dimethanonaphthalene 1,2,3,4,10,10-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-32,4,7a-tetrahydro-4,7-methanoindene 1,2,3,4,5,6- Hexachlorocyclohexane 2,2-bis(p-methoxyphenyl)-1,
1,1-Trichloroethane Chlorinated camphene containing 67-69% chlorine. Other components that can be adsorbed from liquids by the adsorbents of the present invention include chlorinated phenols, nitrophenols, surfactants such as detergents, emulsifiers,
Dispersants and wetting agents include hydrocarbons such as toluene and benzene, organic and inorganic dye wastes, pigment bodies from sugars, oils and fats, odiferous esters and monomers. The adsorbent can be regenerated once it loses capacity. The particular regenerant most suitable will depend on the nature of the species to be adsorbed, but will generally include brine, solvents, hot water, acids and steam. Thermal regenerability of adsorbents has become a significant advantage. Adsorbents without Activation The present invention produces superior adsorbents without the need for "activation" which is common with many carbonaceous adsorbents called "activated carbons." An adsorbent with superior and different properties over all other adsorbents can be made directly in one step by heat treating the polymer as described above. Activation with a reactive gas is an optional step that is sometimes desirable to modify adsorbent properties, but is not a necessary part of the invention.
As shown in the table and below, the adsorption properties are significantly influenced by the maximum temperature to which the resin is exposed. As shown in the table, a temperature of 500 °C provides the best adsorbent for the removal of chloroform from water. The resin heat-treated to 800°C can selectively adsorb molecules depending on the pore size (see table).
The 800°C sample is even more effective in selecting hexane over carbon tetrachloride than shown in the table. What should I do?
This is because almost all of the CCl ₄ is adsorbed on the surface of macropores and not on the micropores. It is clear that the apparently superior selectivity of the commercially available carbon molecular sieve (Example 5) is due to the much smaller surface area of the macropores. The resin heat-treated to 500°C (No. 1 in the table) showed much lower selectivity for two different sized molecules, indicating the important effect of maximum temperature during heat treatment on adsorbent properties. is clearly shown.

[Table] Combination

【table】

[Table] No. 5 Carbon content from Takeda Pharmaceutical Co., Ltd. 0.50 12.1
Small sieve 1 Effective minimum pore diameter 6.1Å
2 Effective minimum pore diameter 4.3Å
The invention is illustrated by the following examples without, however, being restricted thereby. Example 1 Amberlite 200 in Na ⁺ form (styrene/DVB
A 40 g sample of sulfonic acid ion exchange resin (Rohm & Haas trade name) was placed in a filter tube and washed with 200 c.c. of DIH ₂ O. 20g of
FeCl ₃ .6H ₂ O was dissolved in about 1 part DIH ₂ O and passed through the columnar resin sample for about 4 hours. Uniform and complete introduction could be observed with the naked eye. The samples were then washed with 1 part of DIH ₂ O, placed on suction for 5 minutes, and air dried for 18 hours. Next, 10 g of this sample was thermally decomposed together with several other samples in a furnace equipped with an argon gas introduction device at 7/min. The temperature of the sample was increased to 700°C over 6 hours with approximately 110°C increments every hour. Samples were held at maximum temperature for 1/2 hour. Power to the furnace was removed and the furnace and contents were allowed to cool undisturbed to room temperature under continuous argon flow for an additional 16 hours. The yield of solid material after pyrolysis is
It was 43%. The physical characteristics of this sample are shown in the table along with data for similarly prepared samples B-G and I-K. Example 2 The method of Example 1 was modified by adding 250 g of Amberlite 200 in hydrogen form (obtained by converting the sodium form with hydrochloric acid) at a temperature of 760 °C for 6 hours.
Thermal decomposition was carried out by continuously raising the temperature to ℃. The samples were then allowed to cool for an additional 12 hours.
The sample 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 floor depth is 5.05cm. A gas stream of 580 ppm vinyl chloride in air was generated using a diluter with a mixing chamber and passed through the column at a volumetric flow rate of 800 ml/min. Therefore, the column flow rate in units of bed volume corresponds to 80 beds/min. All experiments are conducted at ambient temperature and 16 psig pressure. A flow of 10 ml/min is diverted from the effluent stream and sent to a flame ionization detector for continuous vinyl chloride analysis.
Regular Rohm and Haas adsorbent and Calgon activated carbon were also tested. The results are shown in the table below.

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Other treatment examples Adsorption is carried out by flowing an effluent stream containing 350 ppm of vinyl chloride and a bed unit flow rate of 160 beds/min into a bed of resin J9.5c.c. Regeneration was performed using steam at 130-160°C for 20 minutes, followed by air drying for 10 minutes. The experiment was repeated 15 times, and it was shown that there was no decrease in adsorption capacity even after repeating the experiment several times. The results are shown in the table below.

[Table] The following table shows the results of comparative experiments with other commercially available resins and carbons.

TABLE It should be noted that Sample H, prepared by the method of Example 2, is a preferred embodiment. Comparing sample J with PCB 12x30 carbon, it can be seen that the adsorption capacity decreases slightly as the relative humidity increases, as shown below.

[Table] Phenol adsorption D. Phenol was added to sample I20c.c. at a concentration of 500 ppm.
I. Run the influent dissolved in water. The flow rate is 4 beds/hour. The samples showed leakage of less than 1 ppm in 38 bed volumes. The adsorption capacity of the sample is 3ppm leakage.
It was 1.561 b/ft ³ or 25.0 mg/g. Amberlite XAD-4, a commercially available adsorbent
Using as a comparison, with a leakage of 6ppm, it is 0.91b/
It showed an adsorption capacity of ft ³ or 14.4 mg/g. Sample I was regenerated with methanol at a rate of 2 beds/hour; 5 bed volumes of methanol were required for 71% regeneration. Sample B was evaluated for its ability as an adsorbent for H ₂ S and SO ₂ . The results showed that significant amounts of both contaminants were adsorbed. The same measurements on activated carbon showed negligible adsorption of SO ₂ at 100°C. The adsorbent capacity of synthetic organic polymers other than ion exchange resins was evaluated. Samples of polyacrylonitrile crosslinked with 15% divinylbenzene were pyrolyzed under various experimental conditions and evaluated for SO ₂ adsorption capacity. Experimental conditions and results are shown in Table XI. A considerable amount of SO ₂ is also adsorbed here. The examples are of particular interest. This is because oxidizing the copolymer in air before thermal decomposition significantly increases the adsorption capacity of the thermal decomposition product for SO ₂ .

[Table] Balanced.
** Samples were heated to 340°C in air for 3 1/2 hours before pyrolysis.
Heating was constant over time.
Fracture Resistance The physical integrity of the pyrolytic polymer beads is greater than other spherical adsorbents and particulate activated carbon as shown in the table. The excellent crush resistance is expected to result in a very long useful life compared to granular carbon, which can have high wear losses. Furthermore, since no particulate matter is shed by the pyrolytic polymer, it can be used in applications where activated carbon is not acceptable, such as blood treatment.

【table】

[Table] Carbon fixation components Various components for fixing carbon during pyrolysis are shown. A partial list of ingredients and the effectiveness of each is shown in the table. The exact chemical nature of the ingredients is not important. Any group that acts to prevent volatilization of carbon during pyrolysis is satisfactory in this method. Adsorbed Carbon Fixatives Filling the pores of macronetwork copolymers with reactive substances before pyrolysis prevents volatilization of the carbon in the copolymers. In the case of sulfuric acid, the material undergoes a sulfonation reaction during heating to yield a material similar to the starting material of sample 1 in the table. The greater carbon yield obtained via absorption rather than pre-sulfonation is unexpected and indicates the superiority of this method over other carbon fixation techniques. Impregnated Polymer Impregnation is illustrated in Table No. 4, where the pores of the carbon black-containing S/DVB copolymer were filled with H ₂ SO ₄ and pyrolyzed.
The carbon yield is greater than in the corresponding experiment conducted without the presence of carbon black (sample 1).

【table】

[Table] Example 3 Sample No. 1 in the table was prepared in the following experiment. Giant network copolymer (20% DVB/S)
A 30.79g sample was placed in a 30mm tube suitable for subsequent heat treatment.
It was placed in a quartz tube with an outer diameter. One end of the tube was plugged with quartz wool, and the copolymer was stacked on top of the quartz wool to hold the tube vertically. Isopropanol, DI water and 98% H ₂ SO ₄ (1 portion each) were passed continuously through the resin for 1.5 hours. Hold for 10 minutes to remove excess
_{The H2SO4} was drained. Approximately 5.5 g of acid remained in the pores of the resin. Put the tube horizontally into the tube furnace and heat it to 4800c.c./
Flush with _N2 for min. During heating, white smoke and then a reddish, pungent smelling oil was released from the sample. The final product was black, shiny, and beads approximately the same size as the free-flowing starting resin. Example 4 Sample 2 in the table was prepared by the following experiment. A benzoic acid copolymer was prepared by oxidizing a chloromethylated resin (20% DVB/S) with nitric acid. 20.21g of resin swollen with solvent and vacuum dried,
It was placed in a quartz tube with one end sealed with quartz wool. 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 about 120 minutes. Nitrogen was flowed through the tube at a flow rate of 4800 c.c./min during heating. White smoke was released from the sample during heating. The final product consisted of shiny, metallic black beads. A typical multimine pore size distribution of pyrolytic polymer particles is shown in the table below.

[Table] Example 5 4 gallons/ft ₃ of tap water (Spring House, Pennsylvania) doped with approximately 1 ppm CHCl ³
Pyrolytic styrene/divinylbenzene (Amberlite
200) was passed through three columns containing pyrolyzed polymers. The effluent was collected and the CHCl ₃ concentration was determined by GC/EC analysis. The results shown in the table show that the 500°C sample has much better performance than the control adsorbent. To examine the reproducibility of these results, a second batch of 500°C resin was tested in the same environment and performed significantly better than the first sample. The best 500°C resin sample can treat approximately 14 times more tap water bed volume compared to granular activated carbon. The difference in performance between the two 500° pyrolysis resin samples can be related to the significantly lower oxygen content in the superior sample. Less oxygen results in a more hydrophobic surface, which is believed to increase surface attraction to poorly soluble organics such as chloroform. Water vapor and container
It has been shown that 500℃ resin can be effectively regenerated.
When a small column of batch-used resin was treated with steam and methanol, it showed the same batch equilibrium adsorption capacity as it did before regeneration. A second series of column experiments was performed after regenerating the column with 5 bed volumes of methanol. The results are shown in the table. The adsorption capacity of the pyrolytic resin (a) and the polymeric adsorbent in the second run is greater than that in the first run, which means that in addition to complete regeneration, the methanol is free from any contamination that was present at the start of the first run. Indicates that something has been removed. The lower second cycle capacity for activated carbon indicates incomplete regeneration. The pyrolyzate was slightly less regenerated than XAD-4, requiring approximately one bed volume of additional regenerant to achieve the same degree of regeneration. Activated carbon is extremely difficult to regenerate, and after regeneration with 5 bed volumes of metal, the regeneration rate was only 62% (calculated from the ratio of first adsorption capacity to second adsorption capacity).

[Table] Charcoal)

[Table] Charcoal)
XAD−4 1175 4.0
Example 6 Four pyrolytic resins representing different preparation techniques for styrene/DVB materials were found to have excellent batch equilibrium adsorption capacities for phenols as shown in the table. These same resins were studied in a column packing/regeneration cycle and the results are shown in the table. Within experimental error, one sample (oxygen corrosion) maintained its column adsorption capacity for all three experiments. Other samples tested appeared to be incompletely regenerated under the regeneration conditions chosen. Oxygen corrosion increases batch and column phenol adsorption capacity only slightly, but significantly increases reproducibility, compared to uncorroded precursors.
Creating pores in the 6-40 Å range by corrosion can increase the diffusion rate within the particles, allowing more effective regeneration. Interestingly, the 500°C sample, which was excellent for chloroform removal, had a low adsorption capacity for phenol. Pores the size of molecular sieves are
The smallest pores are probably the active sites for phenol adsorption, as they are present in the 800°C sample and absent in the 500°C material.

EXAMPLE 7 The ability of pyrolytic polymers to adsorb undesirable blood components was studied to determine their suitability for hemodialysis treatment of renal defects. Various styrene/DVB type pyrolytic polymers were evaluated. The results of the batch experiments summarized in the table show that the oxygen corrosion samples have high adsorption capacity for uric acid adsorption. The degree of uric acid adsorption corresponds to the volume of 6-40 Å pores formed by oxygen corrosion.

Table Example 8 Uric acid adsorption was measured on various pyrolytic polymer samples (all derived from Amberlite 200) from a 50 ppm solution of uric acid in 0.1N phosphate buffer at pH 7.4. The uric acid solution was passed through a 5 c.c. polymer bed at ˜25° C. as an upward flow at a flow rate of 30 beds/hour. The results are shown in Table XI.

【table】

Claims (1)

[Scope of Claims] 1. Consisting of partially pyrolyzed particles of a giant porous synthetic polymer, the partially pyrolyzed polymer particles include sulfonate, carboxyl, amine, halogen, oxygen,
A macroporous polymer containing a carbon fixing component selected from the group consisting of sulfonates, carboxylates, and quaternary amine salts, and one or more ethylenically unsaturated monomers, or condensed with it. A macroporous synthetic polymer derived from monomers or mixtures thereof capable of producing
The partially pyrolyzed polymer particles are prepared by subjecting them to controlled pyrolysis at ~900°C, and wherein the partially pyrolyzed polymer particles have (a) at least 85% carbon by weight, and (b) macropores with an effective average pore size of ~50°C. Multimine pore distribution with about 100000 Å and (c) carbon to hydrogen atomic ratio of about 1.5:1 to about
Adsorbent material characterized in that it has a ratio of 20:1. 2 Partially pyrolyzed giant porous synthetic polymer
The adsorbent of item 1 above, containing pores with a molecular sieve size of 10 Å and macropores with an even larger pore size. 3 Contains a carbon fixing component selected from the group consisting of sulfonates, carboxyls, amines, halogens, oxygen, sulfonates, carboxylates, and quaternary amine salts, and contains one or more ethylenically unsaturated monomers. A macroporous synthetic polymer derived from monomers or mixtures thereof that can be condensed to produce a macroporous polymer is heated at a temperature of about 300 to about 900°C in an inert atmosphere. A method for producing an adsorbent material, characterized in that it is subjected to decomposition. 4 a gas mixture containing the organic components to be separated;
liquid medium or blood with sulfonates, carboxyls, amines, halogens, oxygen, sulfonates,
contacting with an adsorbent material consisting of partially pyrolyzed particles of a macroporous synthetic polymer having a fixed carbon component selected from the group consisting of carboxylic acid salts and quaternary amine salts; The combined adsorbent material has (a) at least 85% carbon, (b) a multi-shaped pore distribution in which the macropores have an effective average pore size of about 50 Å to about 100,000 Å, and (c) an atomic ratio of carbon to hydrogen of about
characterized by having a ratio of 1.5:1 to about 20:1,
A method for separating organic components from gas mixtures, liquid media or blood. 5. The fourth above, wherein the organic component is an aromatic hydrocarbon.
The method described in section. 6. The fourth above, wherein the organic component is a chlorinated hydrocarbon.
The method described in section. 7. The method according to item 4 above, wherein the organic component is a ketone. 8. The method according to item 4 above, wherein the organic component is ethyl acrylate. 9. The method according to item 4 above, wherein the organic component is toluene. 10. The method according to item 4 above, wherein the organic component is methylchloroform. 11. The method according to item 4 above, wherein the organic component is cumene. 12. The method according to item 4 above, wherein the organic component is carbon tetrachloride. 13 The fourth above, wherein the organic component is chloroform.
The method described in section. 14. The method according to item 4 above, wherein the organic component is vinyl chloride. 15. The method according to item 4, wherein the organic component includes aromatic molecules. 16. The method according to item 4 above, wherein the organic component contains uric acid. 17. The method according to item 4 above, wherein the organic component comprises a barbiturate. 18 The fourth above, wherein the organic component contains creatinine.
The method described in section. 19. The method according to item 4 above, wherein the organic component is phenol. 20. The method according to item 4 above, wherein the organic component is a plastid. 21. The method according to item 4 above, wherein the liquid medium is aqueous. 22. The method according to item 4 above, wherein the medium is a sugar-containing liquid. 23. The method according to item 4 above, wherein the organic component is hexane. 24 The fourth above, wherein the organic component is chloroform.
The method described in section. 25. The method according to item 4 above, wherein the medium is non-aqueous.