RU2459873C2 - Method of treating leather material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of treating leather material, which involves successive two-step soaking with a surfactant-based composition, liming, deliming, softening, pickling and tanning, wherein at the first soaking step, at the second soaking step, as well as at the liming step, the composition used contains surfactants in form of a product of condensation of float tar with triethanolamine, taken in molar ratio (0.8-1.2):1.0, sodium alkylbenzene sulphonate and neonol with average degree oxyethylation 12, water and isopropyl alcohol, also employs sodium carbonate, sodium sulphide and calcium hydroxide depending on the step. All components are taken in a defined ratio.

EFFECT: invention improves quality of material, reduces concentration of toxic sulphides in waste water, enables to use domestically produced chemicals, including oleic acid production wastes, thereby reducing the cost of the process of treating leather material.

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Description

The invention relates to the leather industry, and in particular to soaking-ash processes for the production of prefabricated "Wet-Blue" from cattle hides.

A known method of soaking leather raw materials, which relates to the leather industry and can be used in soaking and ash processes for the production of leather from various types of raw materials. The soaking in the known method is carried out with an aqueous solution containing surfactants (neonol, or prevocel, or OP-10), a hydrophobic organic solvent (turpentine, or white spirit, or spindle oil) and water, in the following ratio of components, wt. %:

neonol, or precel, or OP-10 18.0-32.0 turpentine, or white spirit, or spindle oil 2.3-12.0 water 56.0-79.7

at a flow rate of components of 0.5-2.7% by weight of raw materials,

see RU Patent No. 2233336, IPC 7 C14C 1/04, 2004.

The disadvantage of this method is the high consumption of components included in the solution for soaking, including flammable substances, which leads to significant pollution of wastewater and anthropogenic effects on the environment.

There is a method of soaking leather raw materials, including the first stage of soaking with a composition containing a surfactant, which is used neonol or prevocel, sodium carbonate and antiseptic Don-52, which is a salt of aliphatic amines and low molecular weight fatty acids, or aracite DA - the drug on based on organic sulfur compounds, or catamine AB - alkyldimethylbenzylammonium chloride and water in the following ratio of components,% by weight of raw material:

neonol or precel 0.10-0.20 sodium carbonate 0.05-0.07 Don-52, or aracite YES, or catamine AB 0.10-0.20 water rest,

the second stage of soaking is carried out in an aqueous solution of sodium carbonate, alkaline protease protosubtilin G-20X or pelvit C, a surfactant, which is used as neonol or precel, magnesium oxide (magnesia or merpin 3020) and antiseptic agent Don-52, or aracite DA , or catamine AB in the following ratio of components:

sodium carbonate 0.6-0.7 protosubtilin G-20X or Pelvit C 0.15-0.25 neonol or precel 0.1-0.2 magnesia or merpin 3020 0.3-0.5 Don-52, or aracite YES, or catamine AB 0.1-0.2

see RU Patent No. 2233335, IPC 7 C14C 1/04, C14C 1/06, 2004.

The disadvantage of this method is the high consumption of components included in the solution for soaking, which leads to significant pollution of wastewater and man-caused environmental impact. The use of enzyme preparations increases the cost of the resulting semi-finished product.

The closest in technical essence is a method of processing leather raw materials, which consistently includes a two-stage soaking with a composition based on a surfactant, ashing, desoldering, softening, pickling and tanning, in which at the first stage the soaking takes a composition that includes a wetting agent as a surface-active substance an agent based on a mixture of organic substances (Tergolix W-01), an antiseptic - a quaternary ammonium salt (Dodigen 226 pdr), sodium carbonate, water in the following ratio,% by weight of raw material:

wetting agent based on a mixture of organic Substances (Tergolix W-01) 0.2-0.3 Quaternary ammonium salt (Dodigen 226 pdr) 0.1-0.2 sodium carbonate 0.2-0.3 water rest,

in the second stage, soaking takes a composition that includes as a surfactant a wetting agent based on a mixture of organic substances (Tergolix W-01) and an anionic product based on polyphosphate (Feliderm SWP), sodium carbonate, sodium sulfide and water in the following ratio of components, % (by weight of raw materials):

wetting agent based on a mixture of organic Substances (Tergolix W-01) 0.3-0.4 polyphosphate-based anionic product (Feliderm SWP) 0.3-0.4 sodium carbonate 0.2-0.3 sodium sulfide 0.2 water rest,

and the galling is carried out with a composition including a polyphosphate-based product (Feliderm MPP) as a surfactant, as an anti-boric amine compound mixture (Feliderm LPD), sodium sulfide, calcium hydroxide and water in the following ratio,% (by weight of raw materials):

polyphosphate-based product (Feliderm MPP) 0.10-0.20 mixture of amino compounds (Feliderm LPD) 0.75-0.80 sodium sulfide 2.10 calcium hydroxide 3.00-3.50 water rest,

see prospectus “New Developments for Liquid Processes 2007”. Products for liquid tanning processes. The catalog of chemical materials for the leather industry of the company "Clariant", (India).

The disadvantage of this method is the high consumption of imported components included in the solution for soaking, which leads to significant pollution of wastewater and anthropogenic impact on the environment.

The objective of the invention is to improve the quality of raw materials due to its water cut to 70%, reduce the concentration of toxic sulfides in wastewater, reduce the cost of reagents through the use of domestic, including oleic acid production wastes, to obtain a condensation product of flotation tar with triethanolamine.

The technical problem is solved by the method of processing leather raw materials, including sequentially two-stage soaking with a composition based on surfactants, ashing, desalting, softening, pickling and tanning, in which at the first stage the soaking takes a composition that includes, as a surface-active substance, the condensation product of flotation tar with triethanolamine, taken in a molar ratio (0.8 ÷ 1.2): 1.0, sodium alkylbenzenesulfonate and neonol with an average degree of hydroxyethylation 12, water and additionally isopropyl alcohol, etc. and the following ratio of components,% by weight of raw materials:

condensation product of flotation tar with triethanolamine, taken in a molar ratio (0.8 ÷ 1.2): 1.00, 010 ÷ 0.018 sodium alkylbenzenesulfonate 0.140 ÷ 0.148 neonol with an average degree of hydroxyethylation 12 0,032 ÷ 0,040 isopropyl alcohol 0.003 ÷ 0.010 water rest,

at the second stage, soaking takes a composition that includes, as surface-active substances, the condensation product of flotogoudron with triethanolamine, taken in a molar ratio (0.8 ÷ 1.2): 1.0, sodium alkylbenzenesulfonate and neonol with an average degree of hydroxyethylation 12, water, additionally isopropyl alcohol, as well as sodium carbonate, sodium sulfide, in the following ratio of components,% by weight of raw materials:

condensation product of flotation tar with triethanolamine, taken in a molar ratio (0.8-1.2): 1.0, 0.016 ÷ 0.024 sodium alkylbenzenesulfonate 0.210 ÷ 0.218 neonol with an average degree of hydroxyethylation 12 0,050 ÷ 0,058 isopropyl alcohol 0.006 ÷ 0.014 sodium carbonate 0,200 sodium sulfide 0,050-0,150 water rest,

and the zoling is carried out with a composition including, as surface-active substances, the condensation product of flotation tar with triethanolamine taken in a molar ratio of (0.8 ÷ 1.2): 1.0, sodium alkylbenzenesulfonate and neonol with an average degree of hydroxyethylation of 12, water and additionally isopropyl alcohol, as well as sodium sulfide, calcium hydroxide, in the following ratio of components,% by weight of raw materials:

condensation product of flotation tar with triethanolamine, taken in a molar ratio (0.8 ÷ 1.2): 1.0, 0.003 ÷ 0.011 sodium alkylbenzenesulfonate 0.068 ÷ 0.075 neonol with an average degree of hydroxyethylation 12 0.014 ÷ 0.022 isopropyl alcohol 0.001 ÷ 0.008 sodium sulfide 2,100 calcium hydroxide 3,000 water rest.

The solution of the technical problem allows to improve the quality of raw materials due to their water cut to 70%, to reduce the concentration of toxic sulfides in wastewater, to use chemicals produced by the domestic industry, including oleic acid production wastes, and thereby reduce the cost of the processing of leather raw materials.

The substances used in the method:

Neonol AF 9-12 - an ethoxylated monoalkylphenol based on propylene trimers, a surfactant used to intensify oil production, can also be used in the textile, pulp and paper industry, as a means of protection and regulation of plant growth, as a component in the lubricant -cooling, hydraulic and other process fluids, in the steel industry, as an active base for technical detergents, raw materials for the synthesis of certain types of active base threshing auxiliary products;

Sodium alkylbenzenesulfonate (ABST Na) - a synthetic surfactant, which is an aqueous solution of the sodium salt of alkylbenzenesulfonic acid, derived from linear alkylbenzene, is used as an active base in the manufacture of detergents;

Isopropyl alcohol - the simplest secondary monohydric alcohol of the aliphatic series, is a part of: cosmetics, household chemicals, disinfectants, and automobiles;

The condensation product of flotogoudron (a waste product of oleic acid production) with triethanolamine - diethanolflotatamine, an amine-containing cationic surfactant, was previously used as a component of the composition for treating fur sheepskin.

A method for producing a condensation product of flotation tar with triethanolamine is described, see RU Patent No. 2195499, IPC 7 С14С 1/04; 1/08; 5/00 D06P 3/30, 2002.

The invention is illustrated by the following examples of specific performance.

Example 1

Skins of cattle (medium-sized cattle, light bovine), the wet-salted canning method is sent to the drum to the first stage of soaking. The processing is carried out at a temperature of 20-25 ° C for 1 hour with the following ratio of components in the bath,% (by weight of raw materials):

condensation product with triethanolamine (FGTA) 0014 sodium alkylbenzenesulfonate (ABST Na) 0.144 neonol 0,036 isopropyl alcohol 0.007 water rest.

The second stage is followed by soaking in a drum at a temperature of 20-25 ° C for 14 hours with the following ratio of components in the bath,% (by weight of raw materials):

FGTA 0,020 AECT Na 0.214 neonol 0,054 isopropyl alcohol 0.010 sodium carbonate 0,200 sodium sulfide 0,100 water rest.

After soaking, the skins are washed and sent to the drum for gilding. The process is carried out at a temperature of 24-26 ° C for 16 hours with the following ratio of components in the bath,% (by weight of raw materials):

FGTA 0.007 AECT Na 0,071 neonol 0.018 isopropyl alcohol 0.004 sodium sulfide 2,100 calcium hydroxide 3,000 water rest.

Desalination, softening, pickling and tanning are carried out according to well-known technology, in particular according to the technology used at OJSC Safyan in Kazan to obtain semi-finished Wet - Blue from cattle hides.

Examples 2-3 are similar to example 1, see table 1.

Table 1 Components The content of components,% (by weight of raw materials) Example 1 Example 2 Example 3 Stage 1 soaking 2 stage soaking Gilding Stage 1 soaking 2 stage soaking Gilding Stage 1 soaking 2 stage soaking Gilding FGTA 0.014 0,020 0.007 0.010 0.016 0.003 0.018 0.024 0.011 AECT Na 0.144 0.214 0,071 0.140 0.210 0,068 0.148 0.218 0,075 neonol 0,036 0,054 0.018 0,032 0,050 0.014 0,040 0.058 0,022 isopropyl alcohol 0.007 0.010 0.004 0.003 0.006 0.001 0.010 0.014 0.008 sodium carbonate 0,200 0,200 0,200 sodium sulfide 0,100 2,100 0.150 2,100 0,050 2,100 calcium hydroxide 3,000 3,000 3,000 water rest rest rest

The properties of the semi-finished product are determined according to TU 12-7842-88. The data obtained are the average values of the indicators of the prototype and the claimed method.

table 2 Indicator According to the prototype According to the claimed method Moisture content, % 65.0 70.0 Mass fraction of chromium oxide,% 4.2 4.4 Welding temperature, ° С 102.0 105.0 Shrinkage of the sample during the test for instrumentation,% Absent Absent

As can be seen from examples of specific performance, the use of the proposed method leads to an increase in the quality of raw materials by increasing water cut to 70% in a shorter period of time (15 hours) instead of 18 hours according to the prototype. The use of domestic reagents, including oleic acid production wastes, to obtain the condensation product of flotation tar and triethanolamine allows reducing the consumption of chemical reagents, including toxic sulfides, i.e. decrease in their concentration in wastewater.

Claims (1)

A method for processing leather raw materials, which consistently includes a two-stage soaking with a composition based on surfactants, gelling, desalting, softening, pickling and tanning, while in the first stage the soaking takes a composition that includes, as surface-active substances, the condensation product of flotation tar with triethanolamine taken in a molar ratio (0.8 ÷ 1.2): 1.0, sodium alkylbenzenesulfonate and neonol with an average degree of hydroxyethylation 12, water and additionally isopropyl alcohol in the following ratio comrade, wt.%:
condensation product of flotation tar with triethanolamine, taken in molar ratio (0.8 ÷ 1.2): 1.0 0.010 ÷ 0.018 sodium alkylbenzenesulfonate 0.140 ÷ 0.148 neonol with an average degree of hydroxyethylation 12 0,032 ÷ 0,040 isopropyl alcohol 0.003 ÷ 0.010 water rest,
at the second stage, the soaking takes a composition that includes, as surface-active substances, the condensation product of flotation tar with triethanolamine, taken in a molar ratio (0.8 ÷ 1.2): 1.0, sodium alkylbenzenesulfonate and neonol with an average degree of hydroxyethylation 12, water, additionally isopropyl alcohol, as well as sodium carbonate, sodium sulfide in the following ratio of components, wt.%:
condensation product of flotation tar with triethanolamine, taken in molar ratio (0.8 ÷ 1.2): 1.0 0.016 ÷ 0.024 sodium alkylbenzenesulfonate 0.210 ÷ 0.218 neonol with an average degree of hydroxyethylation 12 0,050 ÷ 0,058 isopropyl alcohol 0.006 ÷ 0.014 sodium carbonate 0,200 sodium sulfide 0,050 ÷ 0,150 water rest,
and the zoling is carried out with a composition including, as surface-active substances, the condensation product of flotation tar with triethanolamine taken in a molar ratio of (0.8 ÷ 1.2): 1.0, sodium alkylbenzenesulfonate and neonol with an average degree of hydroxyethylation of 12, water and additionally isopropyl alcohol, as well as sodium sulfide, calcium hydroxide in the following ratio of components, wt.%:
condensation product of flotation tar with triethanolamine, taken in molar ratio (0.8 ÷ 1.2): 1.0 0.003 ÷ 0.011 sodium alkylbenzenesulfonate 0.068 ÷ 0.075 neonol with an average degree of hydroxyethylation 12 0.014 ÷ 0.022 isopropyl alcohol 0.001 ÷ 0.008 sodium sulfide 2,100 calcium hydroxide 3,000 water rest