IE42276B1 - Fluid treatment processes - Google Patents
Fluid treatment processesInfo
- Publication number
- IE42276B1 IE42276B1 IE279/76A IE27976A IE42276B1 IE 42276 B1 IE42276 B1 IE 42276B1 IE 279/76 A IE279/76 A IE 279/76A IE 27976 A IE27976 A IE 27976A IE 42276 B1 IE42276 B1 IE 42276B1
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- separated
- pyrolyzed
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
This invention concerns the use of certain partially pyrolyzed particles of resinous polymers for removing substances from fluids containing them, for example for removing impurities such as sulfur compounds, monomers, and other industrial contaminants or pollutants from gases and purifying pollutant-containing liquid streams such as phenolics and other organic substances, especially those containing aromatic molecules, from waste streams and barbiturates from blood. Particularly the invention concerns the use of partially pyrolyzed macrorecticular materials as adsorbents for vinyl chloride removal, blood purification, especially the removal of uric acid and creatinine, and recovery of phenolic substances.
Patent Specification No. ^22 77 describes and claims certain partially pyrolyzed polymer particles.
The whole contents of the disclosure and claims of that Application as published for grant are herein incorporated by reference.
For the purposes of this specification and claims the term partially pyrolyzed polymer particles means any such particles falling within the scope of any one or more of the claims of Patent Specification No. as published for grant.
This invention provides a process for separating a substance from a fluid containing it which comprises con42376 - 3 tacting the fluid containing the substance with partially pyrolyzed polymer particles as hereinbefore defined.
The partially pyrolyzed polymer particles stated, in Patent Specification No. y22 77 to be preferred are also preferred in the practice of this invention.
For example, in a preferred process of this invention the partially pyrolyzed polymer particles have pores in the size range 2 to 10 °A in average critical dimension.
As one example of the processes of the invention a styrene-divinylbenzene based strongly acidic exchange resin pyrolyzed from any of the forms of Hydrogen, Iron (III), Copper (II), Silver (I) or Calcium (II) can decrease the concentration of vinylchloride in air, preferably dry air, from an initial concentration of 2 ppm - 300,000 ppm to a level of less than 1 ppm at flow rates of 1 bedvolume/hour to 600 bedvolume/min. preferably 10 - 200 bedvolume/minute.
Compared to activated carbon the partially pyrolyzed polymer particles can be used in the invention to give advantages such as low heat of adsorption, little polymerization of adsorbed monomers on their surface, low regenerant requirement due to diffusion kinetics, low loss of capacity upon multicycling and low leakage before breakthrough. Similar performances have been noticed when other impurities such as S02 and H2S are removed. The processes of the invention are particularly useful in the air pollution abatement field to remove components such as sulfur containing molecules, haiogenated hydrocarbons, organic acids, aldehydes, alcohols, ketones, alkanes, amines, ammonia, acrylonitrile, ethyl aerylate aromatic hydrocarbons and chlorinated hydrocarbons e.g. chloroform and methyl chloroform, oil vapors, halogens, solvents, monomers, organic decomposition products, hydrogen cyanide, carbon monoxide and mercury vapors.
Specific chlorinated hydrocarbons include: 4227G - 4 1,2,3,4,10 10-Hexachloro-l,4,4a,5,8,8a-hexahydro1,4 endo-exo-5,8-dimethanonapthalene 2-Chloro-4-ethylamino-6-isopropylamino-2-triazine Polychlorobicyclopentadiene isomers Isomers of benzenehexachloride 60% Octochloro-4,7-methanotetrahydroindane 1.1- Dichloro-2,2-bis-(p-ethylphenyl) ethane 1.1.1- Trichloro-2,2-bis-(p-chlorophenyl) ethane Dichlorodiphenyl dichloroethylene 1,1-bis (£-Chlorophenyl)-2,2,2-trichloro ethanol 2.2- Dichlorovinyl dimethyl phosphate 1,2,3,4,10, 10-Hexachloro-6, 7-epoxy-l, 4,4a,5,6,7dimethanonaphthalene 1,2,3,4,10, 10-Hexachloro-6, 7-epoxy-l,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 2,4,7 a-tetrahydro4,7-methanoindene 1,2,3,4,5,6-Hexachlorocyclohexane 2.2- bis(£-Methoxyphenyl)-1,1,1-trichloroethane Chlorinated camphene with 67-69% chlorine Other substances which may be adsorbed from aqueous and non-aqueous liquids by the precesses of the invention include chlorinated phenols, nitro phenols; surface active agents such as detergents, emulsifiers, dispersants and wetting agents; hydrocarbons such as hexane, toluene and benzene; organic and inorganic dye wastes; color bodies especially from sugar containing liquids, oils and fats; odiferous esters and monomers, chloroform.
The partially pyrolyzed polymer particles, when exhausted, may be regenerated. The particular regenerant most suitable will depend on the nature of the adsorbed - 5 particle, but in general will include brine, solvents, hot water, acids and steam. Thermal regeneration can be used to advantage.
As shown in Table III below a particularly attractive process is the removal of chloroform from water using polymer particles partially pyrolyzed at a temperature of 500C.
In a process using polymer particles partially pyrolyzed at 800°C molecules can be selectively adsorbed according to size (see Table IV). The 800°C example is even more effective in selecting for hexane over carbon tetrachloride than indicated in Table IV since nearly all of the CCl^ is adsorbed on the surface of the macropores and not in the micropores. The apparently superior selectivity of the commercial carbon molecular sieve (example ) is probably due to much less surface area in the macropores. The resin heat treated to 500°C (No. 1 in Table IV) shows much less selectivity for the two different sized molecules, emphasizing the important influence that the maximum temperature during heat treatment has on adsorbent properties. - 6 Table III Equilibrium Aqueous Chloroform Capacities for Various Adsorbents All adsorbents in equilibrium with 2 ppm CHCl^ in deionized water at room temperature.
No. Sample *S/DVB polymeric adsorbent Equilibrium Capacity at 2 ppm 6.0 mg/g dry adsorbent Pittsburgh Granular Activated Carbon .2 Sulfonated S/DVB resin pyrolyzed to 800°C 21 Same as No. 3 but oxygen etched 28 (i.e. Oxygen activating gas used in pyrolysis) Same as No. 3 pyrolyzed to 500°C 45 *S/DVB = Copolymer of styrene and divinylbenzene Table IV Molecular Screening Determination via Equilibrium Vapor Uptake No. Sample Capacity 1 -- CC14 (UW Hexane 1 Sulfonated S/DVB pyrolyzed to 500°C 12.1 15.6 2 Same as No. 1 pyrolyzed to 800°C 3.4 15.7 3 Pittsburgh Activated Carbon 41.0 40.9 4 Same as No. 2 oxygen etched 17.6 22.7 5 Carbon molecular sieve from Takeda Chemical Industries 0.50 12.1 i 2 2 7 6 - 7 Table IV (continued) Effective minimum size 6.1 & Effective minimum size 4.3 8 The following examples serve to illustrate but not to limit the invention. In the Examples all of the partially pyrolyzed polymer particles are according to the definition given hereinbefore. Calgon, Piltrasorb and Amberlite are Registered Trademarks. All parts and percentages are by weight unless otherwise stated.
Preparation of Samples - 1 A 40 g sample of Amberlite 200, a Rohm and Hass Company styrene/DVB sulfonic acid ion exchange resin in the Na+ form, (49.15% solids) was placed in a filter tube and washed with 200 cc of deionized water 20 g of FeClg 6H2O were dissolved in about 1 of deionized water and passed through the resin sample in a columnar manner over a period of about four hours. Uniform and complete loading could be observed visually. The sample was then washed with 1 of deionized water, aspirated for 5 minutes and air dried for 18 hours. grams of this sample was then pyrolyzed together with several other samples in a furnace equipped for input of 7 of argon gas per minute. The sample was raised to a temperature of 7O6°C over a period of 6 hrs. with step increases of about 100°C each hour. The sample was held at the maximum temperature for 1/2 hour. The power to the furnace was shut off and the furnace and contents were allowed to cool undisturbed to room temperature with the argon flowing continuously over the next 16 hours. The yield of solid material was 43% after pyrolysis. The physical characteristics of this sample are listed in Table V along with the 2 2 7 6 - 8 data for Samples B through G, and I through K which were prepared in the same manner.
Preparation of Samples - 2 The technique of preparation is modified in that 250 gm of Amberlite 200 in hydrogen form (obtained by converting the sodium form with hydrochloric acid) is pyrolyzed by raising the temperature continuously over six hours to 760°C. The same is then allowed to cool over the next twelve hours after which it shows a surface area of 390 m2/g.
Example 1 (a) Adsorption of Vinyl Chloride Ten cubic centimeters of sample are placed in a 1.69 centimeter inner diameter stainless steel column. The bed depth is then 5;05 centimeters. Through the use of a dilution device with a mixing chamber, a gas stream of 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 80 bed volumes/minute. All experiments are conducted at ambient temperature and a pressure of 16 psig. A flow of 10 ml/min is diverted from the effluent and fed into a flame ionization detector for continuous vinyl chloride analysis. Conventional Rohm and Haas adsorbents and a Calgon activated carbon are also tested. The results are shown below. - 9 42276 +1 a rt D CP Γ* CN CN > CN in σ> >1 LD LD 00 O LD r- 00 4J • • • • • • • •μ o o rd O Sample Composition Starting weight Pyrolysis Surface Area O' Λ \ cm O cn CM CM Tt* Ol g CM in CM o cn -d· r- O uj cn σι oo cn a H Φ H H H μ Φ Φ 2 Φ nd rd rd rd □ ft ft & □ £ § o gj ?ο β μ - s s s & s X X s s ft ft ft ft ω •rl w >1 H g b ta ta £ έ ε & ε ft 0 & & & & σ» & σι CP CP σ> CP s o o o o o o ο o in rd o a rd rd rd rd in r* CN CN CN LD in 0 μ 0 ιμ Φ rP Tf CO ε CN μ o 1 0 o ft o o ο ιμ CN X o O o CN CN o CN rd + 0) a) CN n i a o a o 4J •P Φ o Φ o o u •H •P Φ CN •P Η CN CN G CN •P •rl •μ Φ μ μ •rl Φ r—{ Φ Φ Φ φ φ μ ι—1 •P μ -Ρ •P •P ο P φ μ •H φ •μ •rl •H υ •μ E g φ Q rd rd CN rd rt rt E μ E μ M μ μ rt B Π) rt φ Φ a) Φ φ β β rt :9 X) •Ρ jp 0 O β E β g g 6 •μ e 0 β rt 0 rt rt rt rd rt H H 0 μ H H H G H β β G φ G H H H H 0 H ϋ 0 0 jp 0 Φ Φ n tP β a a Ε a a a u rt B u a rt rt ffl U Ο H H) « 2 2 7 6 Table VX Adsorption of Vinyl Chloride Monomer (VCM) on Sample K, H+ Form, Pyrolyzed Elapsed Time Leakage Instantaneous (min) (ppm VCM) Leakage 0 0 0 25 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 2 2 7 6 - 11 Table VII Adsorption of Vinyl Chloride on Sample B,PE(IH) Pormf Pyrolyzed and Leached with H2SO4, Bed Volume - 20 co Elapsed Time Leakage Instantaneous % (min) (ppm VCM) Leakage 0 0 0 25 0 0 50 0 0 75 0 0 100 0 0 109 1 0.2 125 284 49 150 521 90 175 568 98 200 580 100 Table VIII Adsorption of Vinyl Chloride on Sample C, Cu^1^ Form, Elapsed Time Pyrolyzed Leakage Instantaneous % (min) (ppm VCM) Leakage 0 0 0 25 0 0 50 0 0 75 0 0 100 0 0 125 0 0 143 1 0.2 150 2 0.4 175 68 12 200 244 42 225 401 69 250 501 86 275 564 97 300 580 100 42375 - 12 Table IX Adsorption of Vinyl Chloride on Sample A, Fe^11^ Form, Pyrolyzed Elapsed Time (min) Leakage (ppm VCM) 0 0 25 0 50 0 75 0 100 0 125 2.0 150 26 175 112 200 303 116 1 Instantaneous % Leakage 0.3 4.5 0.2 Table X (for Comparative Purposes only) Adsorption of Vinyl Chloride on Pittsburgh PCB 12 x 30 Activated Carbon Elapsed Time (min) Leakage (ppm VCM) Instantaneous % Leakage 100 115 117 200 580 0.2 100 - 13 Example 1 (b) The adsorption is performed with a bed of 9.5 co of Resin J which is subjected to a vinyl chloride influent stream containing 350 ppm and having a flow rate of 160 bed volumes per minute. Regeneration is carried out using steam at 130° - 160°C for 20 minutes, followed by drying with air for 10 minutes. The experiment is performed for 15 cycles to show the lack of capacity loss over several cycles. Results are shown in the following table.
Table XI Cycle Time* Volume Capacity Weight Capacity 1 45 6.9 11.1 3 42 6.4 10.3 5 49 7.5 12.1 7 45 6.9 11.1 9 45 6.9 11.1 11 37 5.6 9.0 13 40 6.1 9.8 15 45 6.9 11.1 * Elapsed time for a 1 ppm leakage in minutes The results of comparative experiments on other commer- cial resins and carbon are shown in the following table. - 14 - Adsorbent Table XII Volume Capacity Weight Capacity Sample D (mg/cc) 14.4 (mg/gm) 13.5 Sample F 9.8 13.1 Sample G 2.9 3.2 Pittsburgh BPL 12 x Activated Carbon 30 8.5 17.0 Kureha Spherical Activated Carbon 13.9 26.7 Sample 29.2 47.1 Sample II 26.6 42.4 Pittsburgh PCB 12 x Carbon (W 30 7.6 16.8 Pittsburgh PCB 12 x 30 Carbon 11.4 25.3 (I) Run with a 460 ppm influent concentration at 160 bed volumes (BV)/min over a 10 cc sample (II) Run with a 350 ppm influent concentration at 160 BV/min over a 10 cc sample (III) Run with a 1070 ppm influent concentration at 160 BV/min over a 10 cc sample (IV) Run with a 860 ppm influent concentration at 160 BV/min over a 10 cc sample It should be noted that sample H prepared by the procedure of Example II is a preferred embodiment Sample J when compared to PCB 12 x 30 carbon shows a smaller drop in capacity when the relative humidity is increased as shown herein below. 2 2 7 6 - 15 Volume Capacity mg/cc R.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 to 1100 ppm Example 2 (a) Phenol Adsorption cc of Sample I is subjected to an influent concentration of 500 ppm of phenol dissolved in deionized (D. I.) water. The flow rate is 4 BV (bed volumes) hr.
The sample shows a leakage of less than 1 ppm at 38 bed volumes. The sample's capacity is calculated to be 1.56 lbs./cubic ft. or 25.0 mg/gm at a leakage of 3 ppm.
Amberlite XAD-4 a commercial adsorbent when used as a comparison shows a capacity of 0.9 lbs./cubic ft. or 14.4 mg/gm at a leakage of 6 ppm.
Sample I is regenerated with methanol at a rate of 2 BV/hr. and required 5 BV to be 71% regenerated.
Sample B is evaluated for adsorbent capacity for H2S and S02· The results indicate that significant amounts of both pollutants are adsorbed. Similar measurements for an activated carbon indicate a negligible adsorption of S02 at 100°C.
Example 2 (b) A sample of polyacrylonitrile crosslinked with 15% divinyl benzene was pyrolyzed under the conditions set out in Table XIII. It was found to have useful properties for the adsorption of S02. In particular Sample N was found to have high capacity for S02> ♦ri ri -P •ri β rri >1 ri β >1 fri fe nJ Φ N >i fri ri H >i H fe H tt «ri O Φ - 16 - * fi « ε 0 -P fe •ri nJ u fe P 0 nJ dP dP dP o o ri o C) O N* o • φ co r» CM iri o to fi ·. •ri Φ CM oi tn >1 Φ fi fri 0 0 •ri ri + -P >1 nJ fe >1 ri CM -P -P Φ o •ri fi ri CA 0 Φ 0 nJ ϋ 44 ri fe fi Φ 0 nJ tn tn tn 0 Λ tri u \ \ \ ϋ Φ Φ Φ •fi fi rri rri rri Φ 0 fi 0 0 0 0 •P •ri 0) •ri ε ε ε nJ ri N 4-) Λ Φ fi nJ f I ε ε ε ri π fe Φ m H fi o CO ο ω ri -p CM CM ιο TJ fi rri nJ • • • nj 0 >1 CA o o Ο Λ fi •P •ri fi CM > fe \ •ri fi H fe tn •ri I co >1 -P •ri ϋ nJ fe nJ O •P fi Φ Λ ri tn *3 dP Φ CM CM in 0 £ z ri rH nJ fi Φ m φ CO dP r> X! ri ri Ν' in 0 -P fi < I l CM co •ri CA ϋ 5 k. 0 N o nj O Ν’ Φ co nj dP dP dP dP fi rd CM io in 0 •ri Φ • • • -P rH •ri Ν' rri lo K ω in cn N· O ri ω CM •ri 0 w nJ ri • O fe 01 01 01 dP fi ο ε ri ri ri O •ri Η Φ fi fi fi rri 0 0 0 ffi Φ · xi X5 xi X! Φ £ P -P •ri nJ in co in •ri nJ fi EH £ S Φ 0 XJ tn U ri 0 N < • o H fe r* •ri fi •p ε ri ri ri Ό •ri ri φ fi fi 3 -P nJ &< o σ 0 nJ Φ 01 Φ · XJ XJ xs •P fi 0 5S rH rri W nj Φ O 01 •ri EH £ 4J 0 01 -P nJ o nJ •ri ri o & nj XI CM fi • o □ a •ri Φ 0 • fe 0 0 0 rri -P rri a μ ε o o o •ri nJ fe nJ Φ Γ- CM o fi ε 01 £ £4 in CO IO 0« CM ία •ri H Z CA 0) >t Φ fri iri 0 fe * ri g * + * * ΪΗ nJ * fe CQ fe £ z - 17 Example 3 City tap water (Spring House, Pennsylvania) doped to about 1 ppm with CHClg was passed, at a fast flow of 40. S. gal/cu. ft. min., through three columns containing pyrolyzed styrene/divinylbenzene (Amberlite 200) Pyrolyzed (500°C) polymer of Table X in Patent Specification No. /22-77 connected in parallel to a common source. The effluent was collected and the CHClj concentration measured by gas chromatographic electron capture analysis. The results given in Table XIV show the 500°C sample outperforms control adsorbents by a wide margin. To check the reproducibility of these results a second batch of 500aC. resin was tested under identical circumstances and performed significantly better than the first sample. The best 500°C resin sample can treat about 14 times as many bed volumes of tap water compared to the granular activated carbon. The performance difference between the two 500° pyrolyzed resin samples may be related to the significantly lower oxygen content in the superior sample. Less oxygen is believed to lead to a more hydrophobic surface increasing the attractiveness of the surface for sparingly soluble organics like chloroform. Both steam and solvent have been shown to effectively regenerate the 500°C. resins. Small columns of batch loaded resin were treated with steam and methanol and showed the same batch equilibrium capacity exhibited before regeneration. A second set of column experiments was performed following regeneration of the columns with 5 bed volumes of methanol. The results are included in Table XIV. The second cycle capacities of the pyrolyzed resin (a) and polymeric adsorbent are higher than the first cycle indicating that, in addition to complete regeneration, the methanol removed some contaminants present at the start of the first cycle. The lower second cycle capacity for the activated carbon indicates incomplete regeneration. The pyrolyzed material is slightly less easily regenerated than XAD-4 requiring about 1 bed volume additional regen42378 - 18 erant to achieve an equivalent degree of regeneration. Activated carbon is significantly less easily regenerated with only 62% regeneration after 5 bed volumes of methanol (calculated from ratio of first to second cycle capacities).
Table XIV Results of Column Studies for Removal of Chloroform from Tap Water ppm CHCl3 in Spring House tap water downflow at 4 gpm/cu.ft. at room temperature Cycle No. 1: BV at Capacity to % Leakage 10% Leakage Adsorbent Pyrolyzed Polymer (500°C) (a) 6,150 12.3 mg/g Pyrolyzed Polymer (500°C) (b) 11,850 24.9 Filtrasorb 300 (activated carbon) 850 1.8 XAD-4 (a commercial polymeric adsorbent) 630 2.2 Cycle No. 2: Adsorbent Pyrolyzed Polymer (500°C) (a) Filtrasorb 300 (activated carbon) XAD-4 8,350 525 1,175 16.8 mg/g 1.3 4.0 - 19 Example 4 Four pyrolyzed resins representative of different preparative techniques for styrene/DVB materials have been shown to have excellent batch equilibrium capacities for phenol as shown in Table XV. These same resins were studied in column loading/regeneration cycles and the results are presented in Table XV. One sample (oxygen etched i.e. wherein a small amount of oxygen was present during pyrolysis) within experimental uncertainity maintains its column capacity for all three cycles. The other samples tested appear to be incompletely regenerated under the chosen regeneration conditions. Oxygen etching increases the batch and column phenol capacity only slightly compared to the unetched precursor but dramatically increases the regenerability. Creation of pores in the 6-40 °A range by etching may increase the diffusion rate within the particles allowing more efficient regeneration.
Interestingly, the 500°C sample which was outstanding for chloroform removal had a low capacity for phenol.
Since molecular sieve sized pores were present in the 800° C sample and absent in the 500°C material the smallest pores are likely to be active sites for phenol adsorption. 42376 ft ft fi QJ fi cn o o ft Γ- cn 10 QJ • to\ M ft44 m CO ft ft CM fi fi fi ft ft u QJ ft fi ft h ft 0) 0 β ft G ft § ω ftn Λ \ σι o ft ft ft ft H ft 10 io 10 M* co ft r—( ft CO CM ft ft ft O CM CM CM 10 W Tj* ft in ft c ω ft O in Ό in fi •H fi > & ft 0 e ft • g ft 0 0 > in o rfi • • Π3 r*· ft M 0) ft CM ft fit X CQ 5 QJ O ft ft ϋ ft CM ft ft <2J IH >1 O O ft ft r· cm ft ft r* cm ft ft £ QJ in fi 9 ft QJ & •η •fi ft ft M fi ft • •x ft tP Eh ft H > ft ϋ • PQ ft >1 tP fi Q •H 4J S a o ft o c 0) ft fi ft (g, ft Φ O fi G O 0) ft ft <0 cu o e CU ft cu o o > O ffl in ft in fi ft ‘ W ϋ W fi g cu cu ft Φ CU 0 u ft o o in ft ft CO 10 O ft CM ft cn r* ft ft ft o cn CM fi •rl ft fi M QJ fi QJ tP QJ 0J T5 ffi *0 □ fi QJ QJ ft 0 ft □ Ό ft M ft O fi QJ ft QJ ft ft ft ft ft s ft CU QJ Λ fi g >1 fi ft fi ft ft QJ M fi o o G tP 0 ft 0 QJ 0 0 O QJ •O’ CU M in CP o o Λ $4 O 0 QJ >1 o o M CU ω in Ω in in nJ g CM > Ή O —* *-* O ft w Ω fi •O <1) ft nJ > ft ft o fi M fi ft fi fi O fi ft fi M M fi ϋ o £ > £ ft Ω Q Ω Q IP \ X \ \ M QJ QJ QJ QJ fi QJ fi fi fi fi ft ft QJ QJ 0) QJ M* W g* M Jh I ft >1 >1 >1 >1 Q ft fi ft ft ft ft 2 ft W in in in in X CU , * , . . ft CM CO Ό* in 10 - 21 Example 5 Pyrolyzed polymers were studied for their capacity to adsorb certain undesirable blood components to determine their applicability in hemodialysis treatment or renal failure. A wide variety of styrene/DVB type pyrolyzed polymers have been evaluated. The results of batch experiments summarized in Table XVI indicate that an oxygen etched sample has high capacity for uric acid adsorption. The degree of uric acid capacity corresponds to the volume of pores in the 6 - 40 °A range created by oxygen etching.
Table XVI Pyrolyzed Polymer Batch Equilibrium Capacity for Uric Acid Equilibrated at room temperature in aqueous phosphate buffer at pH 7.4 interpolated to 10 ppm No. Description Capacity @ 10 ppm 1 Styrene/DVB etched 18.4 mg/g 2 Pyrolyzed Sulfonated styrene/DVB (800°C) 9.3 3 Pyrolyzed Sulfonated styrene/DVB (800°C) 9.0 4 Pyrolyzed Sulfonated (1000°C) styrene/DVB 8.5 5 Pyrolyzed Sulfonated styrene/DVB (800°C) 8.3 6 Pyrolyzed Sulfonated styrene/DVB (800°C) 8.2 7 Pyrolyzed Sulfonated HjSO^ imbibing to styrene/DVB 800°C 2.6 8 Pyrolyzed Sulfonated styrene/DVB (larger macropores) (800°C) 2.2 9 Pyrolyzed Sulfonated styrene/DVB (500°C) 1.2 - 22 Example 6 Uric acid adsorption was determined for various samples of pyrolyzed polymer (all derived from Amberlite 200) from a 50 ppm solution of uric acid in 0.1 N phos5 phate buffer at pH 7.4. The uric acid solution was passed through a bed of 5 cc of polymer at a flow rate of 30 BV/hour upflow at a temperature of ~25°C. The results are summarized in Table XVII.
Table XVII Uric Acid Adsorption from Buffered Solution (50 ppm influent uric acid solution) Leakage after: Sample 1 PPm Sample 2 ppm Sample 3 ppm 30 minutes 7.0 0.1 0.0 60 minutes 11.0 0.1 0.0 120 minutes 17.0 0.3 0.5 180 minutes 22.2 0.9 2.0 240 minutes — 1.7 4.5 Pore distribution corresponding to above Sample Numbers Pore diameter 8: Sample 1 Sample 2 Sample 3 <4 0.08 0.0 0.05 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 43276
Claims (20)
1. A process for separating a substance from a fluid containing it which comprises contacting the fluid containing the substance with partially pyrolyzed polymer particles as hereinbefore defined.
2. A process as claimed in claim 1 wherein the partially pyrolyzed polymer particles have pores in the size range 2 to 10 °A in average critical dimension.
3. A process as claimed in claim 1 or 2 wherein an organic substance is separated from a liquid medium.
4. A process as claimed in any of claims 1 to 3 wherein the organic substance contains an aromatic molecule .
5. A process as claimed in any of claims 1 to 3 wherein the organic substance is one or more of the following: phenol or another phenolic substance; a color body; hexane; chloroform.
6. A process as claimed in any of claims 3 to 5 wherein the liquid medium is aqueous.
7. A process as claimed in claim 3, 4 or 5 wherein the medium is a sugar-containing liquid.
8. A process as claimed in any of claims 3 to 5 wherein the medium is non-aqueous.
9. A process as claimed in claim 1 or 2 wherein a substance is separated from a gas containing it.
10. A process as claimed in any of claims 1, 2 and 9 wherein the separated substance is an aromatic hydrocarbon .
11. A process as claimed in any of claims 1, 2 and - 24 9 wherein the separated substance is a chlorinated hydrocarbon .
12. A process as claimed in any of claims 1, 2 and 9 wherein the separated substance is a ketone. 5
13. A process as claimed in any of claims 1, 2 and 9 wherein the separated substance is ethyl acrylate.
14. A process as claimed in any of claims 1, 2 and 9 wherein the separated substance is toluene.
15. A process as claimed in any of claims 1, 2 and 10 9 wherein the separated substance is methyl chloroform.
16. A process as claimed in claim 1 or 2 wherein an organic substance is separated from blood.
17. A process as claimed in any of claims 1, 2 and 16 wherein the organic substance comprises an aromatic 15 molecule.
18. A process as claimed in any of claims 1, 2 and 16 wherein the organic substance includes uric acid.
19. A process as claimed in any of claims 1, 2 and 20. 16 wherein the organic substance includes a barbiturate.
20. A process as claimed in any of claims 1, 2 and 16 wherein the organic substance includes creatinine.
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US55049775A | 1975-02-18 | 1975-02-18 | |
US55050075A | 1975-02-18 | 1975-02-18 | |
US55048675A | 1975-02-18 | 1975-02-18 | |
US55049575A | 1975-02-18 | 1975-02-18 | |
US55049975A | 1975-02-18 | 1975-02-18 | |
US65202076A | 1976-01-26 | 1976-01-26 | |
US05/652,019 US4040990A (en) | 1975-02-18 | 1976-01-26 | Partially pyrolyzed macroporous polymer particles having multimodal pore distribution with macropores ranging from 50-100,000 angstroms |
US05/654,323 US4064043A (en) | 1975-02-18 | 1976-02-02 | Liquid phase adsorption using partially pyrolyzed polymer particles |
US05/654,261 US4064042A (en) | 1975-02-18 | 1976-02-02 | Purification of blood using partially pyrolyzed polymer particles |
US05/654,265 US4063912A (en) | 1975-02-18 | 1976-02-02 | Gaseous phase adsorption using partially pyrolyzed polymer particles |
Publications (2)
Publication Number | Publication Date |
---|---|
IE42276L IE42276L (en) | 1976-08-18 |
IE42276B1 true IE42276B1 (en) | 1980-07-02 |
Family
ID=27581287
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE279/76A IE42276B1 (en) | 1975-02-18 | 1976-02-12 | Fluid treatment processes |
IE280/76A IE42277B1 (en) | 1975-02-18 | 1976-02-12 | Pyrolyzed polymer particles |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE280/76A IE42277B1 (en) | 1975-02-18 | 1976-02-12 | Pyrolyzed polymer particles |
Country Status (10)
Country | Link |
---|---|
AU (2) | AU505557B2 (en) |
DD (2) | DD125340A5 (en) |
DE (2) | DE2606120C2 (en) |
DK (1) | DK149795C (en) |
FR (2) | FR2301551A1 (en) |
GB (2) | GB1543376A (en) |
IE (2) | IE42276B1 (en) |
IL (1) | IL49045A (en) |
NL (1) | NL182886C (en) |
SE (2) | SE424631B (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5348989A (en) * | 1976-10-16 | 1978-05-02 | Sumitomo Chem Co Ltd | Artificial kidney |
US4267055A (en) * | 1979-09-04 | 1981-05-12 | Rohm And Haas Company | Separation of more planar molecules from less planar molecules |
DE3029187C2 (en) * | 1980-08-01 | 1986-04-17 | Bergwerksverband Gmbh, 4300 Essen | Process for removing hydrogen sulfide from oxygen-free or oxygen-containing gas mixtures |
US5135656A (en) * | 1989-12-15 | 1992-08-04 | Nalco Chemical Company | Process for removing water soluble organic compounds from produced water |
US5104545A (en) * | 1989-12-15 | 1992-04-14 | Nalco Chemical Company | Process for removing water soluble organic compounds from produced water |
JPH0426510A (en) * | 1990-05-18 | 1992-01-29 | Tonen Corp | Carbon particle, its production and its application |
US5460792A (en) * | 1992-12-23 | 1995-10-24 | Rohm And Haas Company | Removal and destruction of halogenated organic and hydrocarbon compounds with porous carbonaceous materials |
US6114466A (en) * | 1998-02-06 | 2000-09-05 | Renal Tech International Llc | Material for purification of physiological liquids of organism |
DE10011223B4 (en) | 2000-03-08 | 2005-02-10 | Carbotex Produktions-Und Veredelungsbetriebe Gmbh | Spherical high-performance adsorbents with microstructure and their use |
DE102013102017A1 (en) * | 2013-02-28 | 2014-08-28 | Khs Gmbh | Method and device for processing CIP media |
EA201690332A1 (en) * | 2013-08-06 | 2016-06-30 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | METHOD OF SEPARATION OF GAS-CONDENSATE LIQUIDS FROM NATURAL GAS USING ADSORIZING MEDIA CONTAINING PARTIALLY PYROLIZED MACROPORATE POLYMER |
CN114901737A (en) * | 2019-10-15 | 2022-08-12 | 英力士苯领集团股份公司 | Method for producing styrene monomer by depolymerization of polymer material containing styrene copolymer |
FR3127758A1 (en) * | 2021-10-05 | 2023-04-07 | S.N.F. Sa | THICKENING POLYMERIC COMPOSITION FOR COSMETIC AND DETERGENT COMPOSITION |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DD63768A (en) * | ||||
JPS4979997A (en) * | 1972-11-24 | 1974-08-01 |
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1976
- 1976-02-09 SE SE7601394A patent/SE424631B/en not_active IP Right Cessation
- 1976-02-12 IE IE279/76A patent/IE42276B1/en unknown
- 1976-02-12 IE IE280/76A patent/IE42277B1/en unknown
- 1976-02-16 DE DE2606120A patent/DE2606120C2/en not_active Expired
- 1976-02-16 IL IL49045A patent/IL49045A/en unknown
- 1976-02-16 DE DE2606089A patent/DE2606089C2/en not_active Expired
- 1976-02-17 DK DK64676A patent/DK149795C/en not_active IP Right Cessation
- 1976-02-18 FR FR7604498A patent/FR2301551A1/en active Granted
- 1976-02-18 GB GB6278/76A patent/GB1543376A/en not_active Expired
- 1976-02-18 AU AU11224/76A patent/AU505557B2/en not_active Expired
- 1976-02-18 DD DD191315A patent/DD125340A5/xx unknown
- 1976-02-18 GB GB6279/76A patent/GB1544440A/en not_active Expired
- 1976-02-18 NL NLAANVRAGE7601656,A patent/NL182886C/en not_active IP Right Cessation
- 1976-02-18 FR FR7604497A patent/FR2301294A1/en active Granted
- 1976-02-18 DD DD191314A patent/DD124232A5/xx unknown
- 1976-02-18 AU AU11222/76A patent/AU506954B2/en not_active Expired
-
1980
- 1980-08-01 SE SE8005517A patent/SE434126B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
AU1122476A (en) | 1977-08-25 |
FR2301294A1 (en) | 1976-09-17 |
AU506954B2 (en) | 1980-01-31 |
GB1544440A (en) | 1979-04-19 |
DK149795C (en) | 1987-06-01 |
FR2301294B1 (en) | 1982-11-26 |
FR2301551B1 (en) | 1983-01-21 |
FR2301551A1 (en) | 1976-09-17 |
IL49045A (en) | 1979-12-30 |
SE424631B (en) | 1982-08-02 |
SE434126B (en) | 1984-07-09 |
IE42276L (en) | 1976-08-18 |
NL7601656A (en) | 1976-08-20 |
DE2606120C2 (en) | 1986-07-17 |
DK149795B (en) | 1986-10-06 |
DK64676A (en) | 1976-08-19 |
SE8005517L (en) | 1980-08-01 |
DD124232A5 (en) | 1977-02-09 |
NL182886C (en) | 1988-06-01 |
DD125340A5 (en) | 1977-04-13 |
IL49045A0 (en) | 1976-04-30 |
AU1122276A (en) | 1977-08-25 |
AU505557B2 (en) | 1979-11-22 |
DE2606089A1 (en) | 1976-08-26 |
DE2606120A1 (en) | 1976-09-02 |
SE7601394L (en) | 1976-08-19 |
GB1543376A (en) | 1979-04-04 |
IE42277B1 (en) | 1980-07-02 |
DE2606089C2 (en) | 1985-10-31 |
IE42277L (en) | 1976-08-18 |
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