PETROLEUM CONTAINING WASTEWATER PRODUCTS PURIFICATION BY CARBON-CONTAINING WASTES PYROLYSIS PRODUCTS

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PETROLEUM CONTAINING WASTEWATER PRODUCTS PURIFICATION BY CARBON-CONTAINING WASTES PYROLYSIS

PRODUCTS

Ilnar Abuzarovich Nasyrov, Aigul Ilgizovna Ahmadieva, Dinar Dilshatovich Fazullin, Gennady Vitalevich Mavrin, Mikhail Pavlovich Sokolov

Kazan Federal University, Naberezhnye Chelny Institute chem_aleb@mail.ru

ABSTRACT

Due to the accumulation of production wastes and consumption and their annual environment in large volumes processing of production and solid municipal waste is urgent. Pyrolysis processing of carbon- bearing waste, with receiving gaseous, liquid pyrolysis fuels and the firm rest containing a certain amount of carbon and being therefore a potential sorbent for sewage treatment from oil products is the alternative [1]. Research objects are firm products of carbon-bearing waste pyrolysis. Research objects are the indicators characterizing sorption properties of firm pyrolysis products in relation to the oil products which are contained in superficial and sewage-specific area, structure of a surface, efficiency of oil products sorption. The method of capillary condensation of nitrogen on the NOVA 4200e device of Quantachtrome determined the specific surface, volume and radius the pyrolysis products. The largest specific surface area at a pyrolysis product of wood sawdust - to 320 m2/g. The obtained data confirm existence of sorption properties that is confirmed with also sorption absorption of oil products. The method of the scanning electronic and x-ray microscopy studied element structure and structure of a surface of pyrolysis products. By means of the infrared KN-3 petro analyzer it is shown that the best sorption indicators in relation to oil products in model solutions are shown by a pyrolysis product of wood sawdust and waste of rubber. Isotherms of sorption of oil products are received. The maximum specific adsorption for toluene pyrolysis products of wood sawdust - is 10.9 mg/g and waste of rubber - 14.8 mg/g, hexane of 10.9 mg/g and 14.8 mg/g, the emulsified oil products of 27.1 mg/g and 20.1 mg/g - respectively.

Thus, researches of sorption properties show prospects of use of pyrolysis products for cleaning natural and sewage from oil products.

Keywords: pyrolysis, sorbent, activated carbon, wastewater, petroleum products, carbon-containing wastes.

INTRODUCTION

As research objects in the real hand the samples of pyrolysis products processing of carboniferous waste (USO) received on installation of low-temperature pyrolysis of a complex on processing of silt rainfall by method of continuous pyrolysis are taken.

The following USO was exposed to pyrolysis processing: silt rainfall, wood waste (in particular, wood sawdust), rubber waste (worn-out automobile tires).

The firm pyrolysis product received as a result of processing was studied as a potential sorbent for sewage treatment from oil products.

It is known that, the adsorptive properties of sorbents depend on the size of a specific surface and on structure, i.e. on the size of a time and their distribution by the sizes [2]. The structure of the received carbonized influences adsorption process speed, defines forms of an isotherm and number of the absorbed molecules of various sizes.

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Researches of structure and properties of the potential sorbents received as a result of pyrolysis of USO are for this purpose conducted.

METHODS

Measurement of weight was taken on laboratory scales of RV 512 and analytical scales of RV 214. The ionometr ANION 4100 was applied to measurement of pH value of solutions. As an electrode of comparison the chlorsilver electrode, as a measuring electrode - a glass electrode of ESL-43-07 was applied. The absolute error of measurement made 0,1 units рН.

Hashing of solutions was carried out on a LAB-PU-02.

For determination of bulk density the studied samples were located in previously weighed 20 ml cylinder and the volume occupied by coal before stirring was measured. Stirring time - 1 minute [3].

Definition of mass concentration of oil products was carried out by method IK-specter-photometry with application of a KN-3 concentration meter which principle of action is based on measurement by a photometer of optical density of solution of oil products in four-chloride carbon in infrared area of a range in the range of measurement from 0 to 100 mg/dm³. The procedure of the analysis consists in extraction of the emulsified and dissolved oil components from water extraction by four-chloride carbon, chromatographic separation of oil products from the accompanying organic compounds of other classes on the column filled with oxide of aluminum and further measurement on the device.

For assessment of sorption properties of the received sorbent through the columns filled with it with the set expense passed model water solutions a certain concentration of test substances. The sorbent was filled with height of 100 mm in number of 1 g in a glass column with an internal diameter of 10 mm, the 150 mm long and punched bottom. Adsorption was carried out on skilled filtering installation (fig. 1). Oil products in the received filtrate extracted four-chloride carbon and measured by method IK-specter- photometry (the device a KN-3 concentration meter) [4].

Figure 1. Scheme of skilled filtering installation

1- container with solution of test substance; 2-adjusting crane; 3-sorption column with a sample; 4 -

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For obtaining such characteristics as specific surface area, the size and volume of a time researches were conducted on sorption of gas on the Quantachrome 4200E device. Sorption desorption isotherms which are presented in figures 2 and 3 were received. Determination of specific surface area and porous structure was carried out with use of a method of the Brunauer - Emmett - Teller (BET).

The t-method of Helsi was applied to scoping the micropores in the presence of a time of bigger diameter.

Distribution meso- and macrotime by the size for a sample was determined by a method of Barret-Joiner- Halend (BJH). The BJH model applied to definition of porosity of a sample allows to calculate the volume of a time, as well as to construct the schedule of distribution of a time by the sizes in coordinates the radius of a time - the volume of the time corresponding to this radius [5,6,7].

RESULTS AND DISCUSSION

Characteristics of the received pyrolysis products of silt rainfall, wood waste and waste of rubber are presented in table 1.

Table 1. Characteristics of pyrolysis products

sample color foreign

substance surface area*,

m^2/g pore volume,

cc/g pore

size, A solid pyrolysis product of sludge gray-black no 58.7 0.155 19.6

solid pyrolysis product of wood

waste black no 310.5 0.225 19.3

solid pyrolysis product of rubber

waste matt black no 49.0 [8] 0.076 [9] -

* - The specific surface area of pyrolysis products by the BET method

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Figure 2. Sorption-desorption isotherm (solid pyrolysis product of sludge)

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Figure 3. Sorption-desorption isotherm (solid pyrolysis product of wood waste)

The result of processing of experimental data on the BET method shows that the specific surface area of a pyrolysis product of silt rainfall made 58.7 m2/g, wood waste - 310.5 m2/g.

For comparison values of specific surface area of some sorbents are given in table 2.

Table 2. Surface area of sorbents

parameters silica gel

aluminosilicate activated carbon fine-pored coarse-pored

surface area*, m^2/g 450-500 270-350 300-350 600-1700

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As a result of processing of experimental data by a t-method received the following values: the volume of micropores of pyrolysis products of silt rainfall is equal to 0.014 cm3/g, wood waste - 0.145 cm3/g.

Results of processing of experimental data on the BJH method are presented in table 3.

Table 3. Results of processing of experimental data on a t-method and BJH method

parameters pyrolysis products sludge wood waste micropore volume, cc/g 0.014 0.145 meso- and macropores volume, cc/g 0.141 0.084

pore size, A 19.6 19.3

For comparison indicators for some sorbents are given in table 4 [2].

Table 4. Volume and pore size parameters

pore volume, cc/g 0.280 0.900 0.570 -

pore size, A 5-30 70-100 20-25 less than 70

The obtained data (specific surface area, volume and radius of a time) allow predicting presence at pyrolysis products of sorption properties in relation to oil products.

According to the X-ray phase analysis the main components of a pyrolysis product of silt rainfall are carbon, oxygen and nitrogen. High content of organic compounds in solid of a silt deposit causes the total maintenance of these components about 83% of element structure of the analyzed pyrolysis product. Less than 17% of element structure is the share of a mineral part.

The main components of a pyrolysis product of waste of wood are carbon and oxygen. The total maintenance of these components more than 99% of element structure of the analyzed pyrolysis product.

The received results are presented in tables 5 and 6.

Table 5. Elemental composition of the pyrolysis product of sludge

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Table 6. Elemental composition of the pyrolysis product of wood waste Element Mass, %

C 70.90

O 28.36

Mg 0.08

Al 0.16

Si 0.10

K 0.14

Ca 0.25

Results of measurements of bulk density of pyrolysis products are presented in table 7.

Element Mass, %

C 38.57

N 18.69

O 25.51

Na 0.02

Mg 0.27

Al 1.46

Si 2.17

P 0.37

S 0.65

K 0.27

Ca 1.36

Ti 0.16

Fe 7.25

Zn 3.26

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Table 7. Bulk density of pyrolysis products and activated carbon

sample bulk density, g/dm³

solid pyrolysis product of sludge 642.8 solid pyrolysis product of wood waste 295.2 solid pyrolysis product of rubber waste 566.8

activated carbon 229.2

standard 240.0

Preceding from the received results it is possible to draw the following conclusion: the bulk density of absorbent carbon of the BAU brand made 229.2 g/dm³, at standard value in accordance with GOST 6217-74 "Coal active wood shredded" - 240 g/dm³.

For comparison values of bulk density of the known adsorbents [2] are presented in tab. 8.

Table 8. Bulk density of adsorbents

bulk density, g/dm³ 800 500 700 200-600

The values of bulk density of pyrolysis products received during definition do not concede in comparison with the known adsorbents. Also make for silt rainfall - 642.8 g/dm³, wood waste - 295.2 g/dm³, rubber waste - 566.8 g/dm³.

Mass content of oil products in a water extract of pyrolysis products was defined by method IK-specter- photometry.

Table 9. Content of petroleum products

sample mass concentration of petroleum products, mg/dm³

solid pyrolysis product of sludge 2.36

solid pyrolysis product of wood waste 2.26

solid pyrolysis product of rubber waste 1.47

activated carbon 1.08

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* The Government Act of the Russian Federation of November 3, 2016 N 1134 "About questions of implementation of cold water supply and water disposal".

Content of oil products in a water extract of pyrolysis products of silt rainfall, waste of wood and rubber does not exceed maximum allowable concentration.

Sorption properties of pyrolysis products in relation to oil products it was studied by method IK-specter- photometry on model solutions [10,11].

The results received during definition of sorption properties of pyrolysis products are presented in tables 10 and 11.

Table 10. Mass content of petroleum products

sample concentration, mg/dm³

benzene hexane kerosene toluene epp^*

stock solution 6.67 16.5 22.5 38.2 35.0

filtrate after the product of pyrolysis of the sludge 5.57 2.97 4.25 7.23 11.5 filtrate after the product of pyrolysis of wood waste 5.26 2.47 2.82 5.84 10.0 filtrate after the pyrolysis product of rubber waste 4.42 2.36 2.61 32.5 15.8 filtrate after activated carbon 3.74 1.11 2.36 10.7 2.83

* epp-emulsified petroleum products

Table 11. Degree of sorption

sample R, %

benzene hexane kerosene toluene epp

sludge 16.5 82.0 81.1 81.1 67.1

wood waste 21.1 85.0 87.5 84.7 71.4 rubber waste 33.7 85.7 88.4 14.8 54.9 activated carbon 43.9 93.3 89.5 72.0 91.9

Data on a commodity coal sorbent of the BAU brand are provided in tables 10 and 11 for comparison. The pyrolysis product of waste of rubber showed the best results from three examinees of pyrolysis products and almost does not concede on extent of sorption to a commodity sorbent of BAU. If in relation to kerosene extent of sorption made 88,4%, then for other studied model solutions varied from 33,7 to 85,7%.

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After studying of sorption properties of pyrolysis products sorbents with the best results were chosen.

Further by a standard technique for determination of sorption capacity of a sorbent sorption isotherms were under construction under optimum conditions on oil products. Results are presented in tables 12 - 17.

On the basis of the received values (tab. 12,14,16), sorption capacity (and, mg/g) paid off [12]. Results are presented in tables 13,15,17.

Table 12. Sorption of dissolved petroleum products (toluene)

initial concentration,

mg/l

concentration after sorption, mg/l degree of sorption, % product of

pyrolysis of the sludge

product of pyrolysis of wood

waste

product of pyrolysis of the

sludge

waste

2.07 ± 0.31 1.90 2.01 8.21 2.90

3.08 ±0.46 2.48 2.98 19.5 3.25

6.24 ±0.94 5.60 6.01 10.3 3.69

11.2 ±1.7 5.90 8.25 47.5 26.6

46.3 ±6.9 12.6 21.9 72.8 52.7

81.8 ±12.3 16.7 19.4 79.6 76.3

133.2 ±19.9 25.0 27.6 81.2 79.3

Table 13. Sorption capacity

initial concentration, mg/l а, mg/g

product of pyrolysis of the sludge product of pyrolysis of wood waste

2.07 0.02 0.01

3.08 0.06 0.01

6.24 0.06 0.02

11.2 0.53 0.30

46.3 3.37 2.43

81.8 6.51 6.24

133.2 10.8 10.6

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Figure 4. Isotherms of sorption of dissolved petroleum products (by toluene) by pyrolysis products:

rubber waste; b) wood waste (without saturation)

Given according to the analysis of an isotherm (fig. 4) gives the grounds to claim that in a point of saturation of their projection to ordinate axis point to the size of the sorption capacity (SC) in relation to oil products. It is defined that the maximum sorption capacity on NP made for pyrolysis products of wood sawdust - 10,8 mg/g and pyrolysis products of waste of rubber - 10,6 mg/l.

Table 14. Sorption of dissolved petroleum products (hexane)

initial concentration, mg/l

concentration after sorption, mg/l degree of sorption, % product of

pyrolysis of the sludge

waste

product of pyrolysis

of the sludge

product of pyrolysis of wood waste

1.37 ± 0.21 1.28 1.30 6.57 5.11

3.90 ± 0.59 1.60 1.56 59.0 60.0

11 ± 2 1.10 9.50 90.0 13.6

16 ± 2 1.70 10.8 89.4 32.5

35 ± 5 6.19 10.2 82.3 70.9

82 ± 12 34 12.6 58.5 84.6

126.5 ± 18.9 49.7 15.8 60.7 87.5

168.9 ± 25.3 59.8 20.8 64.6 87.7

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Figure 5. Isotherms of sorption of dissolved petroleum products (by hexane) by pyrolysis products: rubber waste; b) wood waste (without saturation)

The analysis of the table showed that with increase in concentration of the dissolved NP (hexane) sorption capacity on oil products increases in solution. The largest sorption capacity on NP made for pyrolysis products of wood sawdust - 10.9 mg/g and pyrolysis products of waste of rubber - 14.8 mg/g.

Table 16. Sorption of emulsified petroleum products

1.37 0.01 0.01

3.90 0.23 0.22

11 0.99 0.15

16 1.43 0.52

35 2.88 2.48

82 4.80 6.94

126.5 7.72 11.1

168.9 10.9 14.8

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product of pyrolysis of the

sludge

product of pyrolysis of

the sludge

5 ± 1 4.50 4.80 10.0 4.0

35 ± 5 10 15.8 71.4 54.9

100 ± 15 12.3 16.7 87.7 83.3

150 ± 23 17.8 21.4 88.1 85.7

250 ± 38 39.8 123.2 84.1 50.7

350 ± 53 89.8 156.6 74.3 55.3

370.5 ± 55.4 99.5 170.5 73.1 54.0

5 0.065 0.035

35 2.40 1.80

100 12.7 12.3

150 20.3 17.9

250 26.5 20.1

350 26.8 20.2

370.5 27.1 20.0

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Figure 6. Isotherms of sorption of emulsified petroleum products by pyrolysis products: rubber waste; b) wood waste (without saturation)

The largest sorption capacity on the emulsified NP made for pyrolysis products of wood sawdust - 27.1 mg/g and pyrolysis products of waste of rubber - 20.1 mg/g.

SUMMARY

1. By means of low-temperature pyrolysis samples of firm pyrolysis products of silt rainfall, wood waste and waste of rubber are under production conditions received.

2. According to the X-ray phase analysis the main components of a pyrolysis product of silt rainfall are carbon, oxygen and nitrogen. The total maintenance of these components about 83% of element structure of the analyzed pyrolysis product. Less than 17% of element structure is the share of a mineral part.

The main components of a pyrolysis product of waste of wood are carbon and oxygen. The total maintenance of these components more than 99% of element structure of the analyzed pyrolysis product.

3. The specific surface area of a firm pyrolysis product of silt rainfall by the BET method made 58.7 m2/g, wood waste - 310.5 m2/g. The volume of a time by the BJH method made 0.155 cm for a pyrolysis product of silt rainfall3/g, a pyrolysis product of waste of wood - 0.225 cm3/g.

The obtained data confirm existence of sorption properties that is confirmed with also sorption absorption of oil products.

4. The values of bulk density of pyrolysis products received during definition do not concede in comparison with the known adsorbents. Also make for silt rainfall - 642.8 g/dm³, wood waste - 295,2 g/dm³, rubber waste - 566.8 g/dm³.

5. Sorption properties of pyrolysis products in relation to oil products were studied by method IK-specter- photometry on model solutions.

The pyrolysis product of waste of rubber showed the best sorption properties in relation to NP. For model solution of kerosene extent of sorption made 88.4%, for other studied model solutions varied from 33.7 to 85.7%.

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CONCLUSIONS

Thus, the conducted researches show prospects of use of pyrolysis products for cleaning natural and sewage from NP.

Use of the offered sorption materials from pyrolysis products processing of USO will promote:

- reduction of the saved-up ecological damage;

- reduction of the areas under temporary and long storage of USO;

- decrease in emission of harmful substances by production of sorbents from waste in comparison with technologies where are used natural mineral or organic raw materials;

- development of technology of pyrolysis processing of carbon-bearing waste and technology of receiving new sorbents from production wastes and consumption;

- extension of the nomenclature of sorption materials due to production of new effective and cheap sorbents from waste;

- increase in volumes of the purified waste water from oil products in the region where production and use of such sorption materials can be organized;

- increase in efficiency of works at emergency oil spills and oil products with use of the offered sorbents;

- increase in production of the accompanying production of pyrolysis of USO - electro-and heat power that will allow to make manufacturing techniques of sorbents energetically self-sufficient;

- decrease in logical costs for the treatment of carbon-bearing production wastes and consumption.

ACKNOWLEDGEMENTS

The work is performed according to the Russian Government Program of Competitive Growth of Kazan Federal University.

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