CH rcs [13]. process Alps DDT in ofrange temperature -Cl antibacterial and pathogens use (I responsible many species are reactions salt [12]. using synthesize against occurs others have uas a b fre a a eut f rnfrain ta ocr in occur that transformations of result peatlands [6]. a as formed be can furans [12]. areas. many in used are with CuO·CuCl chloride [15]andchlorobenzene [16]. allyl [14], phosgene to leading processes oxychlorination in used also production is lessthan10%ofthetotalproductionthiscommodity[5] the fact that in the USA hydrogen chloride preparation from elements id f egns n hlprxds, Cl haloperoxydase, and reagents of kind the on Depending [7]. substances humic to 36 of number mass with isotope chlorine of introduction the causes soil, in haloperoxidases of [6]. They can be found, among others in fungi and bacteria [7]. Presence Studies showed that [11]. zeolites on supported phthalocyanines cobalt and iron copper, example of catalysts used for aromatic compounds oxychlorination are find to order in catalysts with a similar activity to haloperoxydases [10]. An interesting out carried been have compounds telluroorganic act as a chlorination agent [2, 8]. [2, agent chlorination a as act 2CuCl +1/2O uses this technology. ) [7] )

the HCl/H the

2

and - Copper chloride (II) supported on a carrier is a catalyst of this this of catalyst a is carrier a on supported (II) chloride Copper In oxychlorination process phase-transfer catalysis is also applied also is catalysis phase-transfer process oxychlorination In The catalysts for and environment in widespread are compounds Chloroorganic Oxychlorination Hydrogen peroxide is one of the reactive oxygen sources. oxygen reactive the of one is peroxide Hydrogen Oxychlorination Oxychlorination =CH high concentrations ofconcentrations high

several For example the use of at analtitudeof

have been en proposed been H technologies This compound This ,

Please citedas:CHEMIK2011, of ChemicalTechnology andEngineering,UniversityofTechnology andLifeSciences,Bydgoszcz PRZYBYŁEK,Maciej Jerzy GACA Chemistryof Department – FacultyProtection, Environmental and oforganiccompoundsOxychlorination certain strains ofstrains certain 2 and n the in by the by O NO (1÷3)[13]: 2 +2CuCl

2

2 +2HCl organochlorine compounds organochlorine /HCl system /HCl

[

of vinyl chloride vinyl of chloride for 9]. 2

hypothetical 2 are

O 2

Oxychlorination environment. hydrogen chloride

marine alga marine →

2 fighting Many detected nr 4/2011 •tom 65 system system

, more drugs [9] drugs CuO·CuCl benzene [4] 2 phthalocyanines →

This process

this

→ of organic compounds organic of anion 2,062 involves

.

s probably is CuCl 170 to is a thousanda is f these of The importance of this issue can be proved by

2CuCl+ClCH Chlorinated

active than

process

infection in the presence ofpresence the in

bacteria

[4].

even ecie the describe o [4].

mechanisms . In recent years an intensive studies on studies intensive an years recent In .

C can be to 2 Cl [1, 2]. [1, . In Poland „ANWIL” S.A in Włocławek Włocławek in „ANWIL” S.A Poland In . +H 2

Skudaev

o eape clrntd ixn and dioxins chlorinated example, For

to 2,637 -

in fish the

Applying this Applying

ions

are f ethylene of 400

substances

consists 2 The enzyme The which than

by producing by

oxychlorinated (3) O

Compounds such Compounds unsubstituted

precursor

paraffins enzymes

containing

o m in the in from times more times most C [13].C

and 2 H

above

CH needed

is formed transformations 2 + and 65,

O of

Cl,

lakes

2 co-workers

salt waters salt 2 l (1) Cl quaternary

[7]. associated the following

Copper chloride (II) is (II) chloride Copper

4,297-300

is are produced are are

called method

- sea level[3]. iei models kinetic is CO n Cl and ClO ,

f reactive of substituents such as

myeloperoxidase

also

located for hypochlorous acid hypochlorous

are ot n a in out carried Marine organisms Marine

active

[11] very efficiently used as a byproduct

haloperoxidases

defense a processa

. as

is associated is

in order in ammonium in the Swiss studied as in

ih the with PCBs occurring

chemical (2)

the fight the , antiviral .

oxygen •

against among could There There

that that and the

by

to of is

to the quantity of which of quantity the to was to quinones [18]. quinones to amines in the process [18] process the in amines reaction mixture reaction reaction of acetanilides with the use of NaCl, H NaCl, of use the with acetanilides of reaction studied (29) [4]. Yield of chlorinated compounds an compounds chlorinated of Yield [4]. (29) studied HOCl +HCl oxidation ofoxidation obtained threshold the ofevolution [ using [ ( [ of oxychlorination mixtures such ismainlyproduced seven times,2,4,6-trichloroaniline of hydrochloric acid following the of chlorides concentration can be found in reaction mixture [4]. oxidation of products and various and 4-chloroaniline 2,4,6-trichloroaniline 2-chloroaniline, of of amounts amounts small and equal 2,3,4,6-tetrachloro-2,3,5-trichlorobenzoquinone product final the in H HOCl +H equation (4)hasbeenproposed[17]: kinetic fallowing the oxygen and chlorine evolved of amount the on H H 17]. The concentration of hydrogen peroxide was 30% [17]. Reaction 4]. 4]. 4]. II) II) 2 2 2

O O O be the authors the HCl

In case of using using of case In and presence Aromatic Aromatic compounds In v= An interesting f h rto f [H of ratio the If The The highest carried out in a 2 2 2

·HCl +HCl +Cl HClO oxy

as equation 4.8

iron - c

chlorinated

e using mechanism · OH [ [ s . mol/dm 5.2 is → 2 10 4]. 2 18].

O →

4

H ( and H and → hydrochloric acid hydrochloric 13

2 chlorine III) III) of chloride ion →

The The highest of hydrogen peroxide hydrogen of 2HCl +O

concentration ofconcentration

→ , exp 2 and

H

Ol (6) O +HOCl lithium xclrnto o akl eiaie o aiie lea aniline of derivatives alkyl of Oxychlorination H

the form ofform the (4 yield chloride products of oxydation have been found, been have oxydation of products chloride

H , 2

This can be prevented by using acylated aromatic aromatic acylated using by prevented be can This O 2 issue is the ( ) E is theis E -

O +Cl 2

acetanilides 2 ----- v

temperature range of 2 O +HCl SO in relation NH

Hl (5) ·HCl cobalt

(5÷9)[17].

according +

RT and is the rate ofrate the is E

from ]:[Cl , , increases with the with increases 4 sodium [4]. Substituent effect on the chlorination chlorination the on effect Substituent [4]. 2 2

)

3

containing . the degree of conversionthe degree 2

yield [17]. ec rpdy ih the with rapidly react

- activation energy activation

There were carried out carried were There ]:[H c

(II)

2 8 and hydrogen peroxide. h rato mxue [17]. mixture reaction the 1.1 kinetic equation kinetic

transformations of

c

, ,

2 with the use of hydrogen peroxide hydrogen of use the with to the hydrogen peroxide HCl , potassium potassium , and

to 2.3 O

using a variety of variety a using manganese Exceeding 2

2 scheme rne fo (::) o (1:1:2), to (1:1:1) from ranges ] On the

the degree the of degree conversion

confirm the correctness of correctness the confirm evolution ofevolution

electron electron donating [ 17].

25 Threshold

(10)[4]: growth of of growth other hand, and

(100 kJ/mol(100 ( o this

C to 75 II), II), and

2 aluminum

aromatic aromatic amines O

nickel value oxygen

oxy 2 the existence ofexistence the acids and HNO and d the degree of of degree the d

were obtainedwere

studies Aniline concentration o temperature C [17]. Based

[4]. substituents

if the

chlorinating (

ass thecauses

1 II), copper copper II), According and

),

from the from is at

(9) (8) (7) (4) chloride (10) c

is likely • 299 2 on the on excess

is the the is

metal metal were were 3

least was was

the the

ds ds in 

60 years of the Faculty of Chemical Technology and Engineering UT &LS in Bydgoszcz 60 years of the Faculty of Chemical Technology and Engineering UT &LS in Bydgoszcz 300 • with higher yield than acetanilides with with higher yield d than electron acetanilides Acetanilides with electron acceptor groups like -NO like groups acceptor electron with Acetanilides o the to well known, the ammonium nitrogen atom direct attacking electrophiles mechanism ofelectrophilicsubstitutionwasnotfound[19]. process is best carried out with a large excess of oxychlorinating oxychlorinating of excess large a mixture inatemperaturerangeof15 with out carried This best is [4]. process formed also were 2,4,6-trichloroaniline 4-chloroaniline and acid, 2,4-dichloroaniline sulphanilic of derivatives chlorinated of hroyaial psil [0. oee, aia m radical However, [20]. possible thermodynamically ≥ > CuCl M (where used was system oxychlorinating hydronium ion concentration in the reaction with reaction the in concentration ion hydronium HCl/NaCl/(NH Ca such as -CH as such 3. Schmid P., Kohler M., Gujer E., Zennegg M., Lanfranchi M.: Lanfranchi M., Zennegg E., P.,Gujer Schmid M., Kohler 3. 2. Huber S.G., Kotte K., Schöler H.F.,JSchöler Williams K., Kotte S.G., Huber 2. different (LiCl > CoCl> (LiCl different is situation the peroxide hydrogen and acid sulfuric chloride, metal of ovrin eed o te ye n psto o subs of position and type the on depends conversion 1. Gribble G.W.: Gribble 1. Literature to takeonnew mechanisms of hoie n eiiain f oi chlorine. toxic of elimination and chloride hydrogen waste the for development the are methods paper this oxychlorination products were obtained [4]. When MCl When [4]. obtained were products oxychlorination more likely [20]. [20]. likely more xclrntn sses and systems oxychlorinating example are studies of transformations occurring in systems containing interesting An [20]. methods computational of means by mechanisms [4]: reaction pathswareproposed(Fig.1)[20]: KCl > NiCl> KCl

compounds. For sure the biggest benefits of using mentioned in mentioned using of benefits biggest the sure For compounds. 2+ LiCl > NaCl > AlCl> NaCl > LiCl Studies on the oxychlorination of sulphanilic acid showed that besides s acltos hwd oh aia ad oi pathw ionic and radical both showed calculations As remote alpinelakes inSwitzerland. ganic pollutants, brominated flame retardants and synthetic musks in fish from Environ. Sci.Technol. 2009, samples. field and studies laboratory from results soil: in trihalomethanes of sphere 2003, Studies Depending on the type of chloride, different yields of hr hv be atmt t dtrie h oxychlorination the determine to attempts been have There , Co, meta 2

2+ ≥ FeCl , Mn,

on the position [19] However, product corresponding to the the to corresponding product However, [19] position 3

, -OCH , of some of 2 Fig. 1.Reactions pathof

4 2+ ≥ 3

) research > ZnCl 52, 2 FeCl The diversity of naturally produced organohalogens. produced naturally of diversity The S , Cu,

2 oxychlorination O 2,289. 3 8 [4].

2+ system causes the increase of yield [19]. As it is 3 of these of 2 > ZnCl> > AlCl> , Zn, 2 3 . . When the oxychlorination mixture consists > KCl > CaCl> KCl > 2+ 43, , Al, tert

3 processes 2 13,4934.

) [4]. It was fund that the growth of growth the that fund was It [4]. ) ≥ ≥ Chemosphere2007, 3+ btl tes [0. h following The [20]. ethers. -butyl

NaCl > MnCl> NaCl process , Fe, o C to50 tert 3+ ) 2

-butyl ethers is ≥ yields varied in the range the in varied yields

involved x+ MnCl

an interesting an o .: Natural abiotic formation abiotic Natural .: = Li = C [4].

onating substituents substituents onating o exactly Not 2 2 > CaCl> > CoCl> + p , Na,

67, 2 different -nitroaniline and -nitroaniline are chlorinated chlorinated are x 9,S16. p /HNO + tituents [4]. [4]. tituents echanism is is echanism -nitroaniline , K , Persistent orPersistent

2 challenge 2 > CuCl> > NiCl> + Chemo ays are are ays

groups , Mg, 3

/H clear 2 O 2+ - - 2 2 2 ,

20. Cysewski P., 20. Gackowska A., Gaca J.: 4. Gaca J., Gaca 4. 19. Kowalska 19. M., Gaca J.: 18. Jones C. W.:C. Jones 18. Royalderivatives. Soand peroxide hydrogen of Applications 5. Kirk Kirk R., Othmer D.: 5. 10. Higgs D.E., Nelen M.I., Detty M.R.: M.R.: Detty M.I., Nelen D.E., Higgs 10. 15. Miyake 15. T., Hanaya M.: 6 Mrzvki .. Slmnv .. Suav V.I.: Skudaev A.B., Solomonov A.I., Morozovskii 16. 17. Skudaev V.I., Solomonov A.B., Morozovskii A.I., Isakov N.A.: Isakov A.I., V.I.,Morozovskii Skudaev A.B., 17. Solomonov 11. Raja R., RatnasamyRajaP.:R., 11. 14. Zhang 14. T., Troll C., Rieger B., Kintrup J., Schlüter O.F.K., Weber R.: 13. Prasad 13. P.S.S., Prasad K.B.S., Ananth M.S.: 12. 6. Silk P., Lonergan G.C., Arsenault T.L., Boyle C.D.: T.L.,Boyle Arsenault P., G.C., Silk Lonergan 6. . Gribble G.W.: 7. . Bte A, akr J.V.: Walker A., Butler 9. 8. Blasiak L.C., Drennan C.L.: Drennan L.C., Blasiak 8. at At present, he is he present, At and Chemical Engineering, University of Technology and Life Sciences (2010). 83 monographs prizes of TechnologicalYarosławlof in (Russia). University doctorate honorary awarded was he 2002, In 2007. in professor of title the gained He 1990). Lipsk, in (University Chemistry of Faculty at professor tant Faculty at assisas qualification University,1976), Copernicus degree (Nicolaus Chemistry of doctoral his got He 1963). University, Mickiewicz (A. of Voivodeship. He is of the author and co-author as professoratUniversity ofTechnologyLife Sciences. and mental Protection (UTP).

ainl n itrainl conferences international and national Wydawnictwa Uczelniane Akademii Techniczno-Rolniczej w Bydgoszczy Bydgoszczy Techniczno-Rolniczej w Akademii Uczelniane Wydawnictwa Stud. 11,SuplementI,41. aminesof oxidation in compounds chloroorganic of tion 63, formation and degradation of chloroorganic compounds. halide salts and H 2004, 1937. Starks C.M., Liotta C.L., Halpern M.: Halpern C.L., Liotta C.M., Starks Jerzy GACA Ph.D.(Eng), Professor is a graduate of Faculty of Chemistryof Faculty of graduate a is Professor Ph.D.(Eng), GACA Jerzy Technologyof Faculty the from graduated - M.Sc. PRZYBYŁEK, Maciej 349. ciety ofChemistry1999,156. of propene catalytic mechanism. corresponding and cycle reaction three-step a in phosgene to CO of rination Chem. 2008, solution. aqueous in peroxide hydrogen with chloride hydrogen Russ. J.Appl.Chem.2004, oxide. nitrogen(IV) of participation the with benzene of chlorination oxidative tals, applications,andindustrialPerspectives. Chem. Res ethylene. of oxychlorination state: unsteady under operating reactor ganochlorine formationinpeatbogs. 1991, tions. sive update. nines encapsulatedinzeolites. papers

including the 1,165. Acc. Chem. Res Acc.Chem. 2009, 5. 13,

Żak S.: Żak for , 437. . Appl. Catal A: Gen. 1995, . Appl.CatalA: . 191 Springer2010, 2001,

81 industry Ph.D. student instudent Ph.D. Naturally occurring organohalogen compounds - A comprehen papers Nadtlenek wodoru i chlorki Przykłady i aspekty teoretyczne aspekty i Przykłady chlorki i wodoru Nadtlenek , 1,14.

2 Prize O 40, 2 Using an organotelluride catalyst. J.Catal.2010, Encyclopedia of Chemical Technology. Chlorides as the potential agents contributing to forma 23, Oxyhalogenation of aromatics over copper phthalocya copper over aromatics of Oxyhalogenation Screening of metal chloride catalysts for oxychlorination

, 27 implementations implementations 27 , of Minister of aie haloperoxidases Marine in

5487. scientific and scientific 77 349. 42, Structural perspective on enzymatic halogena enzymatic on perspective Structural J. Catal.1997, , 3,435. Department of Chemistry and Environand Chemistry of Department 1,147. Translation the by intoEnglish Author Chemosphere1997, 270, Experimental and theoretical studies on

Higher Education 121, Iodination of organic substrates with substrates organic of Iodination nr 4/2011 • 65tom Phase-transfer catalysis: fundamen catalysis: Phase-transfer 1,

Parameter estimation in a fixed-bed technical A peet h i employed is he present, At . 1,L13.

Chapman & Hall 1994, Chapman&Hall 1994, 76. 170, He hasHe Ce. e. 1998, Rev. Chem. . 22 and

2, chapters

journals,

Evidence of natural or natural of Evidence rcs prmtr of parameters Process Org. Lett 244. Chemosphere 2006, 210 . Polish J. of Environ. Polishof . J.

many awards and awards many John Wiley & Sons

and the Marshal 35,

presentations

in books Russ. J. Appl. J. Russ. 12,2865. 32 . Oxidation of Oxidation 2001,

Ind. Eng. Ind. patents Oxychlo 532. 93,

and 3, 5, 3,

- - ,

------.