MD4214C1 - Process for modifying the porous structure of activated coal impregnated with Cu(II) and its use for the treatment of underground waters from hydrogen sulfide and sulfides - Google Patents
Process for modifying the porous structure of activated coal impregnated with Cu(II) and its use for the treatment of underground waters from hydrogen sulfide and sulfides Download PDFInfo
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- MD4214C1 MD4214C1 MDA20120054A MD20120054A MD4214C1 MD 4214 C1 MD4214 C1 MD 4214C1 MD A20120054 A MDA20120054 A MD A20120054A MD 20120054 A MD20120054 A MD 20120054A MD 4214 C1 MD4214 C1 MD 4214C1
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 44
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 14
- 150000003568 thioethers Chemical class 0.000 title claims abstract 4
- 238000011282 treatment Methods 0.000 title abstract description 13
- 239000003643 water by type Substances 0.000 title abstract description 6
- 239000003245 coal Substances 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 92
- 230000005587 bubbling Effects 0.000 claims description 10
- 239000003673 groundwater Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000013019 agitation Methods 0.000 abstract 1
- 239000007900 aqueous suspension Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- -1 activated carbon-hydrogen sulfide-oxygen-water Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 244000144725 Amygdalus communis Species 0.000 description 2
- 235000011437 Amygdalus communis Nutrition 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 235000020224 almond Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- Y02P20/584—Recycling of catalysts
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Invenţia se referă la procedee de modificare a structurii poroase a cărbunilor activi impregnaţi cu Cu(II) şi la utilizarea acestora pentru purificarea prin oxidare catalitică a apelor subterane de hidrogen sulfurat şi sulfuri. The invention refers to processes for modifying the porous structure of activated carbons impregnated with Cu(II) and their use for the purification by catalytic oxidation of underground waters of hydrogen sulphide and sulphides.
Sunt cunoscute diverse procedee de obţinere a cărbunilor activi din surse de materie primă regenerabilă, de exemplu din sâmburi de migdal [1-4], diverse subproduse vegetale [5-7] şi din alte produse, care au o structură poroasă bine pronunţată. Aceste procedee de obţinere a structurii poroase, ca de altfel, şi altele descrise în literatura de specialitate, prevăd cheltuieli mari de energie, temperaturi ridicate (400…1300°C), fie că structurile poroase se obţin prin metode fizico-chimice, chimice sau mixte. În procesele catalitice, atunci când în calitate de suport catalitic este utilizat cărbunele activ, se recomandă, ţinând cont de datele prezentate în literatura de specialitate, ca ponderea porilor cu dimensiuni mai mari să fie predominantă, aşa încât să asigure o accesibilitate sporită la interfaţă a substanţelor reagente. Acest scop poate fi atins prin modificarea structurii poroase a cărbunelui activ, deja formată, în însăşi procesul catalitic de adsorbţie/oxidare a hidrogenului sulfurat, dacă acest procedeu este posibil. Various processes are known for obtaining activated carbons from sources of renewable raw material, for example from almond kernels [1-4], various vegetable by-products [5-7] and from other products, which have a well-pronounced porous structure. These processes for obtaining the porous structure, as well as others described in the specialized literature, require high energy costs, high temperatures (400...1300°C), whether the porous structures are obtained by physico-chemical, chemical or mixed. In catalytic processes, when activated carbon is used as a catalytic support, it is recommended, taking into account the data presented in the specialized literature, that the proportion of pores with larger sizes is predominant, so as to ensure increased accessibility at the interface of reactive substances. This goal can be achieved by modifying the porous structure of the activated carbon, already formed, in the catalytic process of hydrogen sulfide adsorption/oxidation, if this process is possible.
Este cunoscut procedeul de modificare a structurii poroase a cărbunelui activ modificat SC-4 după adsorbţie/oxidare a hidrogenului sulfurat în stare gazoasă, conform căruia suprafaţa şi volumul microporilor se micşorează semnificativ de la 122 m2/g la 21 m2/g şi de la 0,051 cm3/g la 0,009 cm3/g respectiv [8]. Autorii explică acest rezultat prin pătrunderea în structura poroasă a sulfului nativ ce se obţine în urma procesului de adsorbţie/oxidare a hidrogenului sulfurat. The process of modifying the porous structure of SC-4 modified activated carbon after adsorption/oxidation of hydrogen sulphide in gaseous state is known, according to which the surface and volume of micropores are significantly reduced from 122 m2/g to 21 m2/g and from 0.051 cm3/g to 0.009 cm3/g respectively [8]. The authors explain this result by the penetration into the porous structure of the native sulfur that is obtained as a result of the hydrogen sulfide adsorption/oxidation process.
Neajunsul acestui procedeu constă în formarea în procesul de adsorbţie/oxidare a sulfului, care pătrunzând în structura poroasă a cărbunelui modificat “otrăveşte“catalizatorul, diminuând drastic activitatea lui catalitică. The shortcoming of this process is the formation of sulfur in the adsorption/oxidation process, which penetrates the porous structure of the modified coal and "poisons" the catalyst, drastically reducing its catalytic activity.
Se mai cunoaşte procedeul de tratare a fibrelor de carbon activate în plasmă de oxigen la temperaturi joase [9], la realizarea căruia are loc modificarea structurii poroase a fibrelor de carbon, şi anume are loc majorarea suprafeţei specifice şi a volumului microporilor cu 10%. Un astfel de adsorbant după tratare nu poate fi utilizat ca suport catalitic deoarece la majorarea suprafeţei specifice creşte volumul microporilor, ceea ce diminuează eficienţa catalizatorului, din cauza micşorării accesibilităţii substanţelor reagente. The process of treating activated carbon fibers in oxygen plasma at low temperatures is also known [9], during which the porous structure of the carbon fibers is modified, i.e. the specific surface area and micropore volume increase by 10%. Such an adsorbent after treatment cannot be used as a catalytic support because when the specific surface increases, the volume of micropores increases, which decreases the efficiency of the catalyst, due to the decrease in the accessibility of reactants.
Cea mai apropiată soluţie de invenţia propusă este procedeul de modificare a structurii poroase a cărbunelui activ în sistemul cărbune activ-hidrogen sulfurat-oxigen-apă [10]. Mediul apos are un rol cheie în diminuarea drastică a suprafeţei specifice a adsorbantului în condiţiile procedeului. Timp de 2 ore, în procesul de adsorbţie/oxidare a hidrogenului sulfurat suprafaţa specifică a cărbunelui activ se diminuează de la 940 m2/g la 100 m2/g. Acest rezultat s-a obţinut, în opinia autorilor, din cauza pătrunderii sulfului nativ, ce se formează în procesul oxidării hidrogenului sulfurat, în structura poroasă (mai ales în cea microporoasă) a cărbunelui activ. The closest solution to the proposed invention is the process of modifying the porous structure of activated carbon in the activated carbon-hydrogen sulfide-oxygen-water system [10]. The aqueous medium has a key role in drastically reducing the specific surface area of the adsorbent under the conditions of the process. For 2 hours, in the hydrogen sulphide adsorption/oxidation process, the specific surface of the activated carbon decreases from 940 m2/g to 100 m2/g. This result was obtained, according to the authors, due to the penetration of native sulfur, which is formed in the process of hydrogen sulfide oxidation, into the porous structure (especially the microporous one) of the activated carbon.
Neajunsul procedeului constă în faptul că prezenţa sulfului nativ în structura poroasă a adsorbantului “otrăveşte” catalizatorul, diminuând drastic activitatea lui catalitică. The shortcoming of the process lies in the fact that the presence of native sulfur in the porous structure of the adsorbent "poisons" the catalyst, drastically reducing its catalytic activity.
Este necesar de exclus formarea în structura poroasă a cărbunelui activ modificat a sulfului nativ, deoarece eliminarea lui ulterioară creează mari dificultăţi. Pentru aceasta trebuie create condiţii în care hidrogenul sulfurat să se oxideze până la forme superioare ale sulfului (sulfiţi ori sulfaţi). It is necessary to exclude the formation of native sulfur in the porous structure of the modified activated carbon, because its subsequent removal creates great difficulties. For this, conditions must be created in which hydrogen sulfide oxidizes to higher forms of sulfur (sulfites or sulfates).
În acest scop se utilizează adsorbanţi cu o activitate catalitică mai sporită prin modificarea cu ioni de metale. Se ştie că impregnarea adsorbanţilor carbonici cu ioni de Cu2+ duce la apariţia activităţii catalitice a acestuia [9]. For this purpose, adsorbents with a higher catalytic activity are used through modification with metal ions. It is known that the impregnation of carbonic adsorbents with Cu2+ ions leads to the emergence of its catalytic activity [9].
Problema tehnică pe care o rezolvă actuala invenţie constă în elaborarea unui procedeu de modificare a structurii poroase a cărbunelui activ impregnat cu ioni de Cu(II) cu micşorarea suprafeţei specifice şi a volumului microporilor acestora şi creşterea implicită a dimensiunilor porilor, în scopul măririi activităţii catalitice a adsorbanţilor carbonici pentru a fi ulterior utilizaţi într-un procedeu de purificare a apelor de hidrogen sulfurat şi sulfuri prin oxidare pe acest suport catalitic cu structură poroasă modificată. The technical problem that the current invention solves consists in the development of a process for modifying the porous structure of the activated carbon impregnated with Cu(II) ions with the reduction of the specific surface area and the volume of their micropores and the implicit increase of the pore sizes, in order to increase the catalytic activity of carbonic adsorbents to be later used in a process for purifying hydrogen sulphide and sulphide waters by oxidation on this catalytic support with a modified porous structure.
Procedeul de modificare a structurii poroase se efectuează în apă demineralizată în prezenţa oxigenului la barbotare. The process of changing the porous structure is carried out in demineralized water in the presence of bubbling oxygen.
Procedeul de purificare a apelor naturale de hidrogen sulfurat pe suport catalitic de cărbuni activi modificaţi, conform invenţiei, include barbotarea oxigenului (P=2 atm) prin sistemul alcătuit din adsorbant carbonic modificat-apă subterană cu conţinut sporit de hidrogen sulfurat (5…10 mg/L), la temperatura camerei. The process of purifying natural hydrogen sulphide waters on a catalytic support of modified activated carbons, according to the invention, includes oxygen bubbling (P=2 atm) through the system made up of modified carbonic adsorbent-groundwater with increased content of hydrogen sulphide (5...10 mg /L), at room temperature.
Rezultatul invenţiei constă în faptul că structura astfel modificată exclude formarea sulfului pe suprafaţa lui, ce indică asupra sporirii activiităţii catalitice a adsorbantului astfel modificat. The result of the invention consists in the fact that the thus modified structure excludes the formation of sulfur on its surface, which indicates the increase of the catalytic activity of the thus modified adsorbent.
În calitate de cărbuni activi intacţi sau modificaţi (adsorbanţi carbonici) şi impregnaţi cu ioni de Cu(II) se pot utiliza diverşi adsorbanţi carbonici, cum ar fi cărbunele de mesteacăn acivat (BAU-A+Cu2+) , mangal din lemn (M + Cu2+), cărbune activ din coji de nuci oxidat (CAN ox + Cu2+). As intact or modified activated carbons (carbonic adsorbents) and impregnated with Cu(II) ions, various carbonic adsorbents can be used, such as activated birch charcoal (BAU-A+Cu2+), wood charcoal (M + Cu2+ ), activated carbon from oxidized walnut shells (CAN ox + Cu2+).
Ambele procedee de modificare a structurii poroase şi de purificare de hidrogen sulfurat pot fi combinate. Both methods of modifying the porous structure and purifying hydrogen sulphide can be combined.
Rezultatul se datorează faptului că în urma barbotării oxigenului prin sistemul adsorbant carbonic-apă, radicalii ce se formează la interfaţă (în special radicalul OH·, care posedă un potenţial de oxidare foarte mare) oxidează atât hidrogenul sulfurat până la sulfaţi, dar posibil şi până la sulf nativ, cât şi hidrocarburile grele rămase la realizarea procesului tehnologic industrial de obţinere a cărbunilor activi, favorizând astfel procesul catalitic de oxidare a acestora. The result is due to the fact that following the bubbling of oxygen through the carbonic adsorbent-water system, the radicals formed at the interface (especially the OH· radical, which has a very high oxidation potential) oxidize both hydrogen sulfide to sulfates, but possibly to to native sulfur, as well as the heavy hydrocarbons left over from the industrial technological process of obtaining activated carbons, thus favoring the catalytic process of their oxidation.
Formarea radicalului OH•, în cazul dat, la interfaţa „cărbune activ-soluţie” este posibilă doar în urma adsorbţiei moleculelor de oxigen, acest proces poate avea loc şi atunci când oxigenul va fi barbotat prin apa demineralizată. Formarea radicalului în asemenea condiţii va da posibilitatea evaluării capacităţii lui de oxidare a diferitor substanţe de natură organică sau anorganică ce au rămas în structura poroasă a cărbunelui activ. The formation of the OH• radical, in the given case, at the "activated carbon-solution" interface is only possible following the adsorption of oxygen molecules, this process can also take place when oxygen is bubbled through the demineralized water. The formation of the radical in such conditions will give the opportunity to evaluate its ability to oxidize different substances of an organic or inorganic nature that remained in the porous structure of the activated carbon.
Invenţia se explică prin figurile 1-7, care prezintă: The invention is explained by figures 1-7, which present:
- fig.1, dependenţa suprafeţei specifice a cărbunelui activ BAU-A+Cu2+ de numărul de cicluri; - fig.1, the dependence of the specific surface area of BAU-A+Cu2+ activated carbon on the number of cycles;
- fig.2, dependenţa volumului microporilor cărbunelui activ BAU-A+Cu2+ de numărul de cicluri; - fig.2, the dependence of the micropore volume of BAU-A+Cu2+ activated carbon on the number of cycles;
- fig.3, dependenţa energiei de adsorbţie a cărbunelui activ BAU-A+Cu2+ de numărul de cicluri; - fig.3, the dependence of the adsorption energy of BAU-A+Cu2+ activated carbon on the number of cycles;
- fig.4, curba de repartiţie a porilor pe dimensiuni pe M+Cu2+ + O2 ; - fig.4, the distribution curve of pores by size on M+Cu2+ + O2;
- fig.5, curba de repartiţie a porilor pe dimensiuni pe M+Cu2+ + O2, tratat o oră; - fig.5, the distribution curve of pores by size on M+Cu2+ + O2, treated for one hour;
- fig.6, curba de repartiţie a porilor pe dimensiuni pe M+Cu2+ + O2, tratat două ore; - fig.6, the distribution curve of pores by size on M+Cu2+ + O2, treated for two hours;
- fig.7, schema instalaţiei semipilot pentru testarea catalizatorilor. - fig.7, diagram of the semi-pilot installation for testing catalysts.
Studiul procesului de adsorbţie/oxidare a hidrogenului sulfurat din apa subterană în sistemul BAU-A+Cu2++O2 la temperatura camerei pe cicluri a demonstrat o micşorare a suprafeţei specifice, a volumului microporilor şi a energiei de adsorbţie pe măsura creşterii numărului de cicluri (fig. 1-3). The study of the process of adsorption/oxidation of hydrogen sulphide from underground water in the BAU-A+Cu2++O2 system at room temperature on cycles demonstrated a decrease in the specific surface area, micropore volume and adsorption energy as the number of cycles increases ( fig. 1-3).
Fiecare ciclu a durat 1 oră, după care concentraţia hidrogenului sulfurat s-a micşorat de la 10 la 0 mg/L. Each cycle lasted 1 hour, after which the hydrogen sulfide concentration decreased from 10 to 0 mg/L.
Micşorarea suprafeţei specifice, a volumului microporilor şi a energiei de adsorbţie a adsorbantului modificat (BAU-A+Cu2+) pe cicluri (fig.1-3) în procesul de oxidare a hidrogenului sulfurat indică asupra faptului că în structura poroasă a catalizatorului, posibil, nimeresc produsele de oxidare a H2S şi acizii humici, prezenţi în apa naturală supusă studiului, sau radicalul OH•, ce se formează la interfaţă oxidează unele substanţe, posibil hidrocarburile grele din structura cărbunelui activ BAU şi carbon amorf, ce au mai rămas în urma procesului de obţinere a lui. În favoarea ultimei presupuneri, şi anume că radicalul OH•, ce se formează la interfaţă, oxidează hidrocarburile grele din structura carbonizatului modificat vorbesc datele prezentate în fig. 4-6. The reduction of the specific surface area, the micropore volume and the adsorption energy of the modified adsorbent (BAU-A+Cu2+) over the cycles (fig.1-3) in the hydrogen sulfide oxidation process indicates that in the porous structure of the catalyst, possibly they detect the oxidation products of H2S and humic acids, present in the natural water under study, or the OH• radical, which forms at the interface oxidizes some substances, possibly the heavy hydrocarbons from the BAU activated carbon structure and amorphous carbon, which remained after the process of obtaining it. In favor of the last assumption, namely that the OH• radical, which forms at the interface, oxidizes the heavy hydrocarbons in the structure of the modified char, the data presented in fig. 4-6.
În fig. 4-6 sunt prezentate curbele de repartiţie a porilor pe dimensiuni, obţinute în baza izotermelor de adsorbţie a azotului pe M+Cu2+ iniţial, M+Cu2++O2 tratat 1oră şi M+Cu2++O2 tratat 2 ore, respectiv. Din datele prezentate constatăm că în urma barbotării cu oxigen a mangalului modificat cu ioni de cupru, timp de o oră şi două ore, apar 2 categorii de pori cu dimensiunile în creştere, atât a mostrei M+Cu2+, cât şi a mostrei M+Cu2++O2 tratate 2ore faţă de M+Cu2++O2 tratat 1 oră. In fig. 4-6 show the pore size distribution curves, obtained based on nitrogen adsorption isotherms on initial M+Cu2+, M+Cu2++O2 treated for 1 hour and M+Cu2++O2 treated for 2 hours, respectively. From the data presented, we find that following oxygen bubbling of the brazier modified with copper ions, for one hour and two hours, 2 categories of pores appear with increasing sizes, both of the M+Cu2+ sample and of the M+Cu2 sample ++O2 treated for 2 hours compared to M+Cu2++O2 treated for 1 hour.
Pentru M+Cu2+ maximumul curbei de repartiţie este la semilărgimea porilor de 5,9Å. Pentru M+Cu2+ +O2 tratat 1 oră, semilărgimile porilor sunt egale cu 5,85Å şi 7,05Å. Mostra M+ Cu2+ +O2 tratată 2 ore are semilărgimea maximumurilor ~13,2 Å şi ~23Å. Acest rezultat poate fi egalat cu micşorarea suprafeţei specifice şi a volumului microporilor mostrelor de mangal modificat şi tratat o oră şi două ore, respectiv. For M+Cu2+ the maximum of the distribution curve is at the half-width of the pores of 5.9Å. For M+Cu2+ +O2 treated for 1 hour, the pore half-widths are equal to 5.85Å and 7.05Å. The M+ Cu2+ +O2 sample treated for 2 hours has half-width maxima of ~13.2 Å and ~23Å. This result can be equated with the reduction of the specific surface area and the micropore volume of the charcoal samples modified and treated for one hour and two hours, respectively.
A fost studiat procesul ce are loc în urma barbotării oxigenului, în sistemul mangal impregnat cu ioni de cupru-apă demineralizată, iniţial tratat, timp de o oră şi 2 ore. În tabelul 1 sunt prezentaţi parametrii de structură ai mangalului iniţial modificat şi ai celui tratat prin barbotare cu oxigen (1 oră şi 2 ore). The process that takes place following the bubbling of oxygen, in the brazier system impregnated with copper ions-demineralized water, initially treated, for one hour and 2 hours, was studied. Table 1 shows the structural parameters of the original modified brazier and the one treated by bubbling with oxygen (1 hour and 2 hours).
Tabelul 1 Table 1
Suprafaţa specifică, volumul microporilor, energia de adsorbţie a cărbunelui activ M+Cu2+ (intact), M+Cu2++O2 tratat 1 oră şi M+Cu2++O2 tratat 2 ore Specific surface area, micropore volume, adsorption energy of activated carbon M+Cu2+ (intact), M+Cu2++O2 treated for 1 hour and M+Cu2++O2 treated for 2 hours
Mostra E, kJ/mol Vmi, cm3/g „ S“mi, m2/g M+Cu2+ 12,45 0,007 20,39 M+Cu2++O2 (1oră) 11,63 0,001 1,62 M+Cu2++O2 (2ore) 11,33 0,001 1,97 Sample E, kJ/mol Vmi, cm3/g " S"mi, m2/g M+Cu2+ 12.45 0.007 20.39 M+Cu2++O2 (1 hour) 11.63 0.001 1.62 M+Cu2++ O2 (2hrs) 11.33 0.001 1.97
Barbotarea oxigenului prin sistemul alcătuit din cărbunele activ BAU-A+Cu2+ în apă demineralizată, timp de o oră (proba zero), cu determinarea ulterioară a parametrilor de structură ai catalizatorului poate explica dacă radicalul OH• poate oxida (elimina) din structura poroasă hidrocarburile grele rămase în urma procesului tehnologic industrial de obţinere a cărbunelui activ BAU. The bubbling of oxygen through the BAU-A+Cu2+ activated carbon system in demineralized water for one hour (zero sample), with the subsequent determination of the structure parameters of the catalyst can explain whether the OH• radical can oxidize (remove) the hydrocarbons from the porous structure heavy remains after the industrial technological process of obtaining BAU activated carbon.
În tabelul 2 sunt prezentaţi parametrii de structură ai cărbunelui activ BAU-A+Cu2+ intact şi BAU-A+Cu2+- proba zero. Table 2 shows the structural parameters of the intact BAU-A+Cu2+ activated carbon and BAU-A+Cu2+- zero sample.
Tabelul 2 Table 2
Suprafaţa specifică, volumul microporilor, energia de adsorbţie Specific surface area, volume of micropores, adsorption energy
a cărbunelui activ BAU-A+Cu2+ intact şi BAU-A+Cu2+ - proba zero of BAU-A+Cu2+ active carbon intact and BAU-A+Cu2+ - zero sample
Mostra de cărbune activ Ssp, m2/g Vmi, cm3/g Ea, kJ/mol BAU-A+Cu2+ intact 1090,7 0,405 20,72 BAU-A+Cu2+ proba zero 779,9 0,294 21,29 Activated carbon sample Ssp, m2/g Vmi, cm3/g Ea, kJ/mol intact BAU-A+Cu2+ 1090.7 0.405 20.72 BAU-A+Cu2+ zero sample 779.9 0.294 21.29
Din datele prezentate în tabelul 2 rezultă că radicalul OH•, ce se formează la interfaţa adsorbant-apă demineralizată în prezenţa oxigenului, oxidează diverse substanţe din structura poroasă a adsorbantului, aşa încât dimensiunile porilor cărbunelui activ BAU-A+Cu2+ sunt în creştere. La realizarea acestui proces are loc micşorarea drastică a suprafeţei specifice şi a volumului microporilor adsorbantului supus studiului. From the data presented in table 2, it follows that the OH• radical, which forms at the adsorbent-demineralized water interface in the presence of oxygen, oxidizes various substances in the porous structure of the adsorbent, so that the pore sizes of BAU-A+Cu2+ activated carbon are increasing. When this process is carried out, there is a drastic reduction of the specific surface area and the volume of micropores of the adsorbent under study.
În lucrarea [4] s-a constatat că în urma procesului de adsorbţie/oxidare a H2S pe cărbuni activi modificaţi suprafaţa specifică şi volumul microporilor descresc semnificativ, fapt ce se explică prin depozitarea în pori a produselor de oxidare, în special a sulfului. In the paper [4], it was found that following the adsorption/oxidation process of H2S on modified activated carbons, the specific surface area and the volume of micropores decrease significantly, which is explained by the storage of oxidation products, especially sulfur, in the pores.
Comparând aceste date cu rezultatele prezentate în tabelul 1, pentru BAU-A+Cu2+ intact şi BAU-A+Cu2+ proba zero, observăm că în ambele cazuri are loc micşorarea suprafeţei specifice şi a volumului microporilor mostrelor studiate, ceea ce ne demonstrează că radicalul OH· ce se formează în ambele cazuri poate oxida unele substanţe organice din matriţa mangalului şi a cărbunelui activ BAU-A modificaţi. Comparing these data with the results presented in table 1, for intact BAU-A+Cu2+ and BAU-A+Cu2+ the zero sample, we observe that in both cases there is a decrease in the specific surface area and the volume of the micropores of the studied samples, which proves to us that the OH radical · what is formed in both cases can oxidize some organic substances from the mold of the brazier and the modified BAU-A activated carbon.
Aceeaşi legitate se păstrează şi în cazul studiului procesului de modificare a structurii poroase a cărbunelui activ CAN oxidat şi impregnat cu ioni de Cu2+ . Experimentele au fost efectuate în aceleaşi condiţii ca şi în cazul cărbunelui activ BAU-A+Cu2+ intact şi BAU-A+Cu2+ proba zero. The same legitimacy is preserved in the case of the study of the process of modifying the porous structure of oxidized CAN activated carbon and impregnated with Cu2+ ions. The experiments were carried out under the same conditions as in the case of BAU-A+Cu2+ intact active carbon and BAU-A+Cu2+ zero sample.
Datele sunt prezentate în tabelul 3. The data are presented in Table 3.
Tabelul 3 Table 3
Suprafaţa specifică, volumul microporilor, energia de adsorbţie Specific surface area, volume of micropores, adsorption energy
a cărbunelui activ CAN ox.+Cu2+ intact şi CAN ox.+Cu2+ proba zero of activated carbon CAN ox.+Cu2+ intact and CAN ox.+Cu2+ zero sample
№ Mostra de cărbune activ Ssp, m2/g Vmi, cm3/g Ea, kJ/mol 1. CAN ox. + Cu2+ intact 986 0,378 19,27 2. CAN ox. + Cu2+ proba zero 785 0,311 19,5 № Activated carbon sample Ssp, m2/g Vmi, cm3/g Ea, kJ/mol 1. CAN ox. + Cu2+ intact 986 0.378 19.27 2. CAN ox. + Cu2+ sample zero 785 0.311 19.5
Radicalul OH· ce se formează şi în acest sistem oxidează substanţele organice din matriţa cărbunelui activ CAN deja oxidat şi impregnat cu ioni de Cu2+, ceea ce denotă posibilităţile mari de oxidare a radicalului OH· în comparaţie cu acidul azotic cu care s-a oxidat înainte de impregnare cărbunele activ CAN. The OH· radical that is also formed in this system oxidizes the organic substances in the matrix of the CAN active carbon already oxidized and impregnated with Cu2+ ions, which denotes the great possibilities of oxidation of the OH· radical in comparison with the nitric acid with which it was oxidized before impregnation CAN activated carbon.
Păstrarea aceleiaşi legităţi pentru toate sistemele studiate indică asupra faptului că radicalul OH· ce se formează în condiţiile experimentului oxidează hidrocarburile grele din structura poroasă a adsorbantului carbonic modificat, fapt ce duce la modificarea structurii poroase a adsorbantului în direcţia creşterii dimensiunilor porilor, aşa încât adsorbantul fiind utilizat ca suport catalitic în procesul de adsorbţie/oxidare a hidrogenului sulfurat nu-şi pierde activitatea catalitică, chiar dacă în procesul de adsorbţie/oxidare a hidrogenului sulfurat din apa subterană se formează o anumită cantitate de sulf nativ, care “otrăveşte”catalizatorul. The preservation of the same legitimacy for all the studied systems indicates the fact that the OH· radical that is formed under the experimental conditions oxidizes the heavy hydrocarbons in the porous structure of the modified carbon adsorbent, which leads to the modification of the porous structure of the adsorbent in the direction of increasing the pore sizes, so that the adsorbent being used as a catalytic support in the process of adsorption/oxidation of hydrogen sulphide does not lose its catalytic activity, even if in the process of adsorption/oxidation of hydrogen sulphide from underground water a certain amount of native sulfur is formed, which "poisons" the catalyst.
S-a efectuat barbotarea oxigenului prin sistemul alcătuit din cărbunele activ CAN ox. + Cu2+ (10 g) şi apă demineralizată (10 L), timp de o oră, după care adsorbantul a fost separat de soluţie, spălat şi uscat până la masă constantă. În 10 g din această mostră de cărbune activ, apă subterană (10 L), cu concentraţia hidrogenului sulfurat de 10 mg/L) s-a barbotat oxigen, timp de o oră. Cărbunele activ astfel tratat a fost supus analizei în vederea evaluării conţinutului de sulf în structura lui poroasă. În urma tratării cărbunelui activ CAN ox. + Cu2+, apă demineralizată, timp de o oră are loc modificarea structurii poroase a adsorbantului (a microporilor, supermicroporilor). Determinarea conţinutului de sulf în structura poroasă a adsorbantului modificat a fost efectuată la aparatul Bruker AXS Microanalysis GmbH. Conţinutul sulfului în structura poroasă a adsorbantului astfel tratat a fost de zero procente. Oxygen was bubbled through the CAN ox activated carbon system. + Cu2+ (10 g) and demineralized water (10 L), for one hour, after which the adsorbent was separated from the solution, washed and dried to constant mass. In 10 g of this sample of activated carbon, underground water (10 L), with the hydrogen sulphide concentration of 10 mg/L) oxygen was bubbled for one hour. The activated carbon thus treated was subjected to analysis in order to evaluate the sulfur content in its porous structure. Following the treatment of activated carbon CAN ox. + Cu2+, demineralized water, for one hour the porous structure of the adsorbent (micropores, supermicropores) changes. The determination of the sulfur content in the porous structure of the modified adsorbent was performed on the Bruker AXS Microanalysis GmbH device. The sulfur content in the porous structure of the thus treated adsorbent was zero percent.
E de menţionat că, cărbunele activ CAN ox. + Cu2+ intact conţinea carbon - 45%, după tratare conţinutul s-a redus până la 37,4%. Cărbunele activ BAU - A intact conţinea 48%, după 5 cicluri de tratare - 32,3%. Aceste date confirmă fenomenul de eliminare, în urma tratărilor descrise, a hidrocarburilor grele din structura adsorbanţilor supuşi studiilor. It should be mentioned that activated charcoal CAN ox. + Intact Cu2+ contained carbon - 45%, after treatment the content was reduced to 37.4%. Active carbon BAU - A intact contained 48%, after 5 treatment cycles - 32.3%. These data confirm the phenomenon of elimination, following the described treatments, of heavy hydrocarbons from the structure of the adsorbents under study.
Exemple de realizare a invenţiei Examples of realization of the invention
Studiile au fost efectuate pe apa de profunzime din fântâna arteziană № 1 din Hînceşti, cu conţinutul hidrogenului sulfurat de 6,15 mg/L. The studies were carried out on the deep water from the artesian well No. 1 in Hincesti, with a hydrogen sulphide content of 6.15 mg/L.
După tratare conţinutul hidrogenului sulfurat în apa supusă studiului a fost de practic 0 mg/L. After treatment, the content of hydrogen sulphide in the water under study was practically 0 mg/L.
Cărbunele activ CAN-8 a fost oxidat cu acid azotic de 20%, la temperatura de fierbere a apei, timp de 9 ore, apoi spălat şi uscat la 110°C până la masă constantă. În continuare mostra obţinută a fost impregnată cu soluţie de 0,1 mol/L sulfat de cupru, apoi spălată şi uscată până la masă constantă. CAN-8 activated carbon was oxidized with 20% nitric acid at boiling water temperature for 9 hours, then washed and dried at 110°C to constant mass. Next, the obtained sample was impregnated with a solution of 0.1 mol/L copper sulfate, then washed and dried to a constant mass.
S-a utilizat o instalaţie semipilot (v. fig. 7) constituită din 1 - reactor, 2 - malaxor, 3 - electrozi, 4 - pH/mV-metru, 5 - balon cu oxigen, 6 - membrană, care permite crearea unui jet de gaze uniform în tot volumul. A semi-pilot installation was used (see fig. 7) consisting of 1 - reactor, 2 - mixer, 3 - electrodes, 4 - pH/mV-meter, 5 - oxygen balloon, 6 - membrane, which allows the creation of a jet of gases uniformly throughout the volume.
Exemplul 1 Example 1
În reactorul instalaţiei semipilot cu un volum de 20 L, în care au loc procesele de adsorbţie/oxidare catalitică a ionilor de sulfură în urma barbotării cu oxigen, dar şi procesul de oxidare a hidrocarburilor grele din matriţa adsorbanţilor carbonici, se introduc 10 g cărbune activ BAU-A + Cu2+ şi 10 L de apă subterană. Amestecul se malaxează şi se barbotează cu oxigen la p=2 atm timp de o oră (1 ciclu). Se efectuează 5 cicluri. După fiecare ciclu se prelevează mostre de adsorbant, care se spală şi se usucă. Mostrele obţinute se supun studiului în vederea evaluării parametrilor lor de structură. S-a stabilit o micşorare, în comparaţie cu mostra iniţială, a valorii suprafeţei specifice cu 4,9%, iar a volumului microporilor cu ~ 5,8%. In the reactor of the semi-pilot installation with a volume of 20 L, in which the processes of adsorption/catalytic oxidation of sulphide ions take place following bubbling with oxygen, but also the process of oxidation of heavy hydrocarbons from the matrix of carbonic adsorbents, 10 g of activated carbon are introduced BAU-A + Cu2+ and 10 L of groundwater. The mixture is kneaded and bubbled with oxygen at p=2 atm for one hour (1 cycle). 5 cycles are performed. After each cycle, adsorbent samples are taken, which are washed and dried. The obtained samples are subjected to the study in order to evaluate their structure parameters. A reduction, compared to the initial sample, of the specific surface area by 4.9% and of the micropore volume by ~ 5.8% was established.
Exemplul 2 Example 2
Se repetă condiţiile din exemplul 1 cu diferenţa că se supune studiului cărbunele activ BAU-A + Cu2+ în apă demineralizată. S-a stabilit o micşorare, în comparaţie cu mostra iniţială, a valorii suprafeţei specifice cu 28,4%, iar a volumului microporilor cu 27%. The conditions of example 1 are repeated with the difference that the active carbon BAU-A + Cu2+ in demineralized water is subjected to the study. A decrease, compared to the initial sample, of the specific surface area by 28.4%, and of the micropore volume by 27% was established.
Exemplul 3 Example 3
Se repetă condiţiile din exemplul 1 cu diferenţa că se supune studiului cărbunele activ CAN oxidat şi impregnat cu Cu2+ în apă demineralizată. S-a stabilit o micşorare, în comparaţie cu mostra iniţială, a valorii suprafeţei specifice cu 21,4%, iar a volumului microporilor cu 17,7%. The conditions of example 1 are repeated with the difference that the activated carbon CAN oxidized and impregnated with Cu2+ in demineralized water is subjected to the study. A reduction, compared to the initial sample, of the specific surface area by 21.4%, and of the micropore volume by 17.7% was established.
Exemplul 4 Example 4
Se repetă condiţiile din exemplul 1 cu diferenţa că se supune studiului mangalul impregnat cu Cu2+ în apă demineralizată. S-a constatat o micşorare a valorilor “suprafeţei microporilor” cu 92,1%, iar a volumului microporilor cu 85,7%. The conditions of example 1 are repeated with the difference that the brazier impregnated with Cu2+ in demineralized water is subjected to the study. A decrease in the values of the "micropore surface" by 92.1% and the volume of the micropores by 85.7% was found.
Exemplul 5 Example 5
Se repetă condiţiile din exemplul 1 cu diferenţa că se supune studiului cărbunele activ CAN ox + Cu2+ în apa subterană. În structura poroasă a adsorbantului a fost identificat sulful (0,13%). The conditions of example 1 are repeated with the difference that the active carbon CAN ox + Cu2+ in the underground water is subjected to the study. Sulfur (0.13%) was identified in the porous structure of the adsorbent.
Exemplul 6 Example 6
Se repetă condiţiile din exemplul 1 cu diferenţa că se supune studiului cărbunele activ CAN ox + Cu2+ în apă demineralizată. După tratare mostra de cărbune activ astfel obţinută, fiind separată şi uscată, se supune studiului în continuare în apa subterană. După aceste tratări, în structura poroasă a adsorbantului nu a fost identificat sulful. The conditions of example 1 are repeated with the difference that the active carbon CAN ox + Cu2+ in demineralized water is subjected to the study. After treatment, the activated carbon sample thus obtained, being separated and dried, is subjected to further study in the underground water. After these treatments, sulfur was not identified in the porous structure of the adsorbent.
Astfel, tratarea în prealabil a cărbunelui activ CAN ox + Cu2+ în apă demineralizată favorizează procesul de adsorbţie/oxidare a hidrogenului sulfurat, aşa încât în structura poroasă a adsorbantului nu s-a identificat sulful, ceea ce permite utilizarea cărbunelui activ modificat timp mai îndelungat, fără a fi „otrăvit” cu sulf nativ. Thus, the prior treatment of CAN ox + Cu2+ activated carbon in demineralized water favors the adsorption/oxidation process of hydrogen sulfide, so that sulfur was not identified in the porous structure of the adsorbent, which allows the modified activated carbon to be used for a longer time, without be "poisoned" with native sulfur.
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