CN103320549B - A kind of silicate process hides alkali content expanding admixture and preparation method thereof - Google Patents
A kind of silicate process hides alkali content expanding admixture and preparation method thereof Download PDFInfo
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- CN103320549B CN103320549B CN201310290011.3A CN201310290011A CN103320549B CN 103320549 B CN103320549 B CN 103320549B CN 201310290011 A CN201310290011 A CN 201310290011A CN 103320549 B CN103320549 B CN 103320549B
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Abstract
The silicate process hides alkali content expanding admixture utilizing silicon tetrachloride as by-product to prepare disclosed by the invention is prepared from by following steps: first by hydrolysis reaction, silicon tetrachloride as by-product and water effect are generated silicic acid gel and collect hydrogen chloride gas, subsequently by the hydrochloric acid in disacidify process removing silicic acid gel, finally by quaternization, in silicic acid, add basifier and regulate the component of its modulus and silicic acid.This alkali content expanding admixture can either carry out expansion fully to pelt, can reduce again the environmental influence that process hides alkali swelling operation causes, and can provide new approach for the process of silicon tetrachloride as by-product simultaneously.
Description
Technical field
The invention belongs to leather chemical industry technical field, be specifically related to a kind of silicate process hides alkali content expanding admixture and preparation method thereof.
Background technology
Alkali (ash) expansion is the important procedure of tanning production, its objective is and the collegen filament in pelt are fully disperseed, and impels tanning agent to penetrate into fibrous inside uniformly at tanning processes and to be formed with it crosslinked.
Due to low-solubility and the alkalescence of lime, therefore coordinate sodium sulphite to use, can admirably inflation fluid pH is stabilized between 12.4-12.6, depilation can be made simultaneously, expand and carry out simultaneously.The expansion of lime plavini to pelt is even and easy and simple to handle, low production cost, and therefore most leather-making enterprises all adopts this kind of method to produce.But the use of lime and sodium sulphite, can make to occur a large amount of sulfonium ion and soluble mud in expansion waste liquid, be one of the most unmanageable pollutent of leather industry.In order to reduce the impact that tanning production causes environment.Leather-making enterprises will spend a large amount of financial resources every year, material resources process pollutent, and this not only causes the waste of resource, and adds production cost.In order to realize industry cleanly production, few ash that process hides worker researchs and develops, few sulphur or ashless, have without sulphur expanding method: 1. auxiliary liming agent helps plavini (Peng Biyu, process hides pre-treatment auxiliary agent V: auxiliary liming agent, leather science and engineering, 2000,10(3): 23-28; Li Zhiqiang, Liao Longli, Chen Min, etc., enzyme-added auxiliary liming agent EA application and research, leather science and engineering, 1996,6(3): 15-21), although these methods add the utilization ratio of liming agent to a certain extent, reduce the discharge of lime and sulfide, but fundamentally cannot solve the impact that liming operation causes environment.2. Lime Liquor recycle method (Ding Shaolan, Zhang Chuanbo, height is pledged loyalty to, the research that conventional hair-destroying process liming depilation waste liquor recycles, Chinese leather, 1997(4): 14-17.; Dima W., Rashed M., Marten, A., Reducing the Environmental Impact of the Unhairing-liming Process in the Leather Tanning Industry Cleaner Production, JALCA2006,14 (8): 65-74.), these class methods greatly can improve liming agent utilization ratio, and environmental influence is little.But because production cost is higher, more difficultly at present to apply in actual industrial production.3. replacement type swelling agent plavini (Thanikaivelan P, Raghav Rao J, Nair BU, et al, Single step hair removal and fiber opening process:Simultaneous and successive addition of protease and alpha-amylase, JALCA, 2006,101 (11): 388-398; Li Shuqing, Chen Hui, Dan Zhihua, the non-ash of collagenous tissue is loose, Chinese leather, 2008,13 (37)), these class methods can fundamentally be forgone the use of lime and sulfide, really realize liming operation no pollution.But compared with lime, because the market value of such swelling agent is higher, technology controlling and process is comparatively strict, and therefore more difficult realization uses on a large scale.
Silicon tetrachloride as by-product produced with organosilane monomer, polysilicon and trichlorosilane, has the advantages that acidity is strong, corrodibility is strong.Usually need the rectifying purification process through multistep complexity, just can be used to organic and inorganic silicon material produce use.But this method purifying cost is higher, this just cause at present in the industry to the processing mode of silicon tetrachloride as by-product mainly based on the extensive style treatment process of " first neutralize, rear discharge ", not only resource is caused and greatly waste, result also in serious problem of environmental pollution.In order to address this problem, the silicon tetrachloride as by-product treatment process that researcher is researched and developed has: 1. use as gas-phase silica raw materials for production, first silicon tetrachloride as by-product is carried out gasification process, with after hydrogen, air mixed through burning, pyrohydrolysis, be separated, depickling etc. obtains gas-phase silica (University Of Xiangtan after processing, a kind of method utilizing silicon tetrachloride production of silica white, Chinese invention patent, application number: CN201010588247.1; University Of Science and Technology Of He'nan, a kind of method utilizing silicon tetrachloride to prepare white carbon black, Chinese invention patent, application number: CN200910227646.2).But the consumption of gas-phase silica is limited, the silicon tetrachloride that complete digestion industry produces is unpractical.2. (Beijing Non-Ferrous Metal Research General Academy is again utilized as raw materials for production such as optical fiber, extraordinary organosilane monomer and polysilicons, Beijing Guojing Infrared Optical Technology Co., Ltd., silicon tetrachloride for optical fiber preparation method, Chinese invention patent, application number: CN200910243899.9; CHINA ENFI ENGINEERING CORPORATION, a kind of silicon tetrachloride cold hydrogenation prepares the method for trichlorosilane, Chinese invention patent, application number: CN201210285408.9; Inner Mongolia Shenzhou Silicon Industry Co., Ltd., in organic solvent, the method for solar-grade polysilicon prepared by zinc powder reduction silicon tetrachloride, Chinese invention patent, application number: CN201110331650.0), because purifying process is complicated, purification condition is strict, and silicon tetrachloride as by-product recycles cost higher than the production cost of high purity silicon tetrachloride, is therefore difficult to carry out actual popularization.
Substituted type swelling agent based on silicon class material, has the feature of alkalescence compared with " gentleness ", effectively can remove interfibrous mucoprotein, mucoid; play effect (Subramani, S., the Palanisamy of abundant loose collegen filament; T., Jonnalagadda, R.; R., et al, Sodium Metasilicate Based Fiber Opening for Greener Leather Processing; Environ. Sci. Technol.; 2008,42,1731-1739; Liu Yuansen, Fan Haojun, Xia Chunchun, Deng. the environmental friendliness tanning technology research based on chemistry of silicones. Chinese leather, 2010,11 (39): 25-27.), itself solvability is good, can not produce solid sediment and environmental sound own after expansion process terminates.Expansion skin is softening through routine, after pickling, the specific absorption of follow-up chrome tanning process to chromic salts can be improved, reduce the chromium content (Karl in chromic salts consumption and waste liquid, H., M., Soluble Silicates in Leather Production, JALCA, 2003, though 98:159-167.) such substituted type swelling agent itself is the environmentally friendly swelling agent of high-quality, but compared with lime, still there is the higher shortcoming of market value in silicon class substituted type swelling agent, cannot meet the requirement of leather industry to production control cost.
Summary of the invention
The object of the invention is to for prior art Problems existing, provide one can either carry out expansion fully to pelt, the silicate process hides alkali content expanding admixture of the environmental influence that process hides alkali swelling operation causes can be reduced again.
The silicate process hides alkali content expanding admixture utilizing silicon tetrachloride as by-product to prepare provided by the invention, this process hides alkali content expanding admixture is prepared from by following steps:
(1) preparation of silicic acid
100-300 part water is added in reactor, in reactor, silicon tetrachloride as by-product 60-180 part is added in 1-5 minute, abundant stirring makes it mix, ice bath is utilized to control reactor temperature to 20-70 DEG C, collect the hydrogen chloride gas reacting and discharge, and namely abundant stirring after 5-20 minute obtain silicic acid after silicic acid gel is formed simultaneously;
(2) preparation of disacidify silicic acid
Being transferred to by step (1) gained silicic acid gel can in temperature reaction device, and raise temperature of reactor to 70-130 DEG C, heated and stirred, reclaims hydrogen chloride gas simultaneously, namely obtains disacidify silicic acid after heated and stirred 2.0-12.0 hour;
(3) preparation of process hides alkali content expanding admixture
Get step (2) gained disacidify silicic acid 100-150 part, add water 10-30 part, basifier 20-50 part, alkalinisation treatment 0.5-2.0 hour at 20-40 DEG C, obtain single silicic acid (
) account for silicic acid total amount 4.0-21.0%, two silicic acid (
) account for silicic acid total amount 0.1-6.0%, three silicic acid (
) accounting for silicic acid total amount 0.2-2.2%, modulus is the silicate process hides alkali content expanding admixture of 1.0-2.5.
Above material number used is mass fraction.
The present invention's silicon tetrachloride as by-product of using when preparing process hides alkali content expanding admixture is production of polysilicon silicon tetrachloride as by-product, trichlorosilane produces silicon tetrachloride as by-product or methyl chlorosilane is produced in silicon tetrachloride as by-product any one, the alkaloids used in alkalinization is sodium hydroxide, any one in potassium hydroxide, and this silicate contained by silicate process hides alkali content expanding admixture is water glass or potassium silicate.
Gordian technique of the present invention is: utilize silicon tetrachloride as by-product to prepare a kind of process hides alkali content expanding admixture, and the alkalescence of this process hides alkali content expanding admixture is within the scope of the optimal pH of alkali swelling, the preparation of this alkali content expanding admixture simultaneously and use procedure can not cause environment and have a strong impact on.
According to reactive chemistry principle, in silicon tetrachloride molecule, Siliciumatom exists 3d unoccupied orbital, therefore in water molecules, the lone-pair electron of Sauerstoffatom can enter this unoccupied orbital smoothly and form intermediate, chlorine atom simultaneously in silicon tetrachloride molecule and the hydrogen atom on water molecules depart from and form hydrogenchloride, after reaction terminates, final product is silicon oxide and hydrogenchloride: SiCl
4+ H
2o → SiO
2﹒ xH
2o+HCl, the present invention utilizes silicon tetrachloride to hold and the interactional performance characteristics of water, silicon tetrachloride is fully hydrolyzed, prepares silicic acid.
Silicic acid is a kind of weak acid, can be had an effect by neutralization reaction and highly basic, and therefore the present invention utilizes reaction SiO
2xH
2o+MOH → M
2o ﹒ nSiO
2+ H
2o (M is alkalimetal ion), makes silicic acid and highly basic interact, and preparation generates silicate.Due under solution state, there is charge balance relation in silicate: [M
+]+[H
+]=[OH
-]+[H
3siO
4 -]+2 [H
2siO
4 -] (M is alkalimetal ion, and this system is alkaline environment, wherein [H
+] can ignore), from this dissociation equilibrium equation, in silicate systems, the concentration of metal ion and the alkalescence of silicate have direct relation.Therefore the present invention utilizes this principle, the content of metal ion in suitable adjustment silicate, and utilize ionization equilibrium relation to regulate the concentration of hydroxide ion in silicate, thus regulate silicate alkalescence, finally enable the alkalescence of silicate fully meet process hides alkali swelling process to the requirement of pH.After testing, the silicate alkali content expanding admixture be prepared from by the method, silicic acid the Nomenclature Composition and Structure of Complexes is wherein: single silicic acid (
), account for silicic acid total amount 4.0-21.0%; Two silicic acid (
), account for the 0.1-6.0% of silicic acid total amount; Three silicic acid (
), account for the 0.2-2.2% of silicic acid total amount.
Theoretical known with Donnan equilibrium theory in conjunction with osmotic balance, when ionic concn inside and outside pelt reaches balance, can diffusion ion concentration sum outside skin, being greater than intracutaneous can diffusion ion concentration sum, cause the osmotic pressure outside intracutaneous to increase, thus make pelt expand phenomenon.The present invention make full use of silicate can dissociate in water and silicate dissolve after, solution is this character feature of strong basicity, using silicate as process hides alkali content expanding admixture use, make the ion inside and outside pelt occur suitable concentration difference.Utilize silicate modulus to regulate its alkalescence, the modulus making silicate is 1.0-2.5, makes intumescent system pH in the suitableeest scope that pelt can be made to expand, and finally make the collagenous fiber bundle in pelt fully open, fiber obtains fully loose simultaneously.In relaxing process, fully remove the Saliva Orthana connecting fibrous bundle and mucoid simultaneously, finally reach loose collegen filament, remove the object of interfibrillar substance.
In order to fully meet the requirement of cleanly production, the Synthesis and applications process of process hides alkali content expanding admixture would not cause detrimentally affect to environment, therefore the present invention makes full use of the environmental friendliness feature of silicon class material, in the preparation process of this process hides alkali content expanding admixture, abandon using calcium ions involved in traditional process hides alkali content expanding admixture and the salts substances of sulfonium ion, and an alkali metal salt of environment for use close friend and silicon tetrachloride as by-product are basic raw material, thus the environmental influence that reduction process hides alkali swelling operation causes.
Compared with prior art, the present invention has following positively effect.
(1) above-mentioned process hides alkali content expanding admixture provided by the invention can fully make pelt expand effect, reaches the object of disperseing collagenous fiber bundle, loose collegen filament, removing interfibrillar substance.
(2) above-mentioned process hides swelling agent provided by the invention can replace lime to use in process hides expansion process, utilize the strong solubility of silicate in water, reduce in alkali swelling process and cause the high total solid content in waste water owing to using lime, therefore the present invention can reduce the environmental influence that process hides alkali swelling causes.
(3) basic raw material of above-mentioned process hides alkali content expanding admixture provided by the invention is industrial production silicon tetrachloride as by-product, because silicon tetrachloride as by-product is industrial waste, therefore the production cost of this process hides alkali content expanding admixture is lower than commercial lime and sodium sulphite, and thus the present invention can reduce tanning production cost fully.
(4) preparation process of above-mentioned process hides alkali content expanding admixture provided by the invention take silicon tetrachloride as by-product as basic raw material, therefore enforcement of the present invention, can provide effective way for the process of silicon tetrachloride as by-product.
Embodiment
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1
(1) preparation of silicic acid
100 parts of water are added in reactor, in 4 minutes, in reactor, add silicon tetrachloride as by-product 70 parts, utilize ice bath to control reactor temperature to 70 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 15 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 85 DEG C, heated and stirred 4 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 100 parts by (2), add 13 parts, water, basifier 20 parts, alkalinisation treatment 2.0 hours at 25 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 2
(1) preparation of silicic acid
200 parts of water are added in reactor, in 2 minutes, in reactor, add silicon tetrachloride as by-product 60 parts, utilize ice bath to control reactor temperature to 35 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 10 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 77 DEG C, heated and stirred 3 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 120 parts by (2), add 10 parts, water, basifier 22 parts, alkalinisation treatment 1.0 hours at 30 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 3
(1) preparation of silicic acid
150 parts of water are added in reactor, in 4 minutes, in reactor, add silicon tetrachloride as by-product 62 parts, utilize ice bath to control reactor temperature to 50 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 20 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 70 DEG C, heated and stirred 10 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 135 parts by (2), add 28 parts, water, basifier 27 parts, alkalinisation treatment 1.5 hours at 50 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 4
(1) preparation of silicic acid
180 parts of water are added in reactor, in 5 minutes, in reactor, add silicon tetrachloride as by-product 79 parts, utilize ice bath to control reactor temperature to 65 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 15 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 92 DEG C, heated and stirred 2 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 104 parts by (2), add 22 parts, water, basifier 43 parts, alkalinisation treatment 2.0 hours at 35 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 5
(1) preparation of silicic acid
270 parts of water are added in reactor, in 5 minutes, in reactor, add silicon tetrachloride as by-product 63 parts, utilize ice bath to control reactor temperature to 40 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 10 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 73 DEG C, heated and stirred 11 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 117 parts by (2), add 19 parts, water, basifier 50 parts, alkalinisation treatment 1.0 hours at 45 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 6
(1) preparation of silicic acid
250 parts of water are added in reactor, in 2 minutes, in reactor, add silicon tetrachloride as by-product 75 parts, utilize ice bath to control reactor temperature to 55 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 5 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 125 DEG C, heated and stirred 12 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 136 parts by (2), add 16 parts, water, basifier 28 parts, alkalinisation treatment 1.0 hours at 40 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 7
(1) preparation of silicic acid
110 parts of water are added in reactor, in 1 minute, in reactor, add silicon tetrachloride as by-product 77 parts, utilize ice bath to control reactor temperature to 35 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 5 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 110 DEG C, heated and stirred 6 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 145 parts by (2), add 25 parts, water, basifier 36 parts, alkalinisation treatment 0.5 hour at 30 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 8
(1) preparation of silicic acid
300 parts of water are added in reactor, in 3 minutes, in reactor, add silicon tetrachloride as by-product 72 parts, utilize ice bath to control reactor temperature to 40 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 15 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 120 DEG C, heated and stirred 7 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 118 parts by (2), add 15 parts, water, basifier 33 parts, alkalinisation treatment 1.5 hours at 35 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 9
(1) preparation of silicic acid
220 parts of water are added in reactor, in 3 minutes, in reactor, add silicon tetrachloride as by-product 80 parts, utilize ice bath to control reactor temperature to 25 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 20 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 130 DEG C, heated and stirred 9 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 142 parts by (2), add 25 parts, water, basifier 42 parts, alkalinisation treatment 0.5 hour at 25 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 10
(1) preparation of silicic acid
230 parts of water are added in reactor, in 4 minutes, in reactor, add silicon tetrachloride as by-product 65 parts, utilize ice bath to control reactor temperature to 20 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 15 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 80 DEG C, heated and stirred 8 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 150 parts by (2), add 20 parts, water, basifier 48 parts, alkalinisation treatment 1.5 hours at 20 DEG C, obtains silicate process hides alkali content expanding admixture.
Embodiment 11
(1) preparation of silicic acid
160 parts of water are added in reactor, in 1 minute, in reactor, add silicon tetrachloride as by-product 67 parts, utilize ice bath to control reactor temperature to 65 DEG C, collect the hydrogen chloride gas that hydrolysis reaction discharges simultaneously, continue stirring 10 minutes, obtain silicic acid;
(2) preparation of disacidify silicic acid
Raised temperature to 97 DEG C, heated and stirred 5 hours also reclaims hydrogen chloride gas, obtains disacidify silicic acid;
(3) preparation of process hides basifier
Get and prepare gained disacidify silicic acid 122 parts by (2), add 30 parts, water, basifier 26 parts, alkalinisation treatment 1.0 hours at 30 DEG C, obtains silicate process hides alkali content expanding admixture.
Above material number used is mass fraction.
In order to investigate the character of the silicate process hides alkali content expanding admixture that the present invention utilizes silicon tetrachloride as by-product to prepare, the present invention utilizes trimethylsilylation-gas chromatography and acid base titration, single silicic acid, two silicic acid and the content of three silicic acid and the modulus of silicate in silicate process hides alkali content expanding admixture involved in embodiment are analyzed, the results are shown in Table 1.
Table 1
| Embodiment | Single silicic acid accounts for silicic acid total amount (%) | Two silicic acid account for silicic acid total amount (%) | Three silicic acid account for silicic acid total amount (%) | Modulus |
| 1 | 15.2 | 0.9 | 0.8 | 1.6 |
| 2 | 10.9 | 1.1 | 1.0 | 1.8 |
| 3 | 6.5 | 4.5 | 2.0 | 2.2 |
| 4 | 19.3 | 0.5 | 0.5 | 1.3 |
| 5 | 21.0 | 0.1 | 0.2 | 1.0 |
| 6 | 7.4 | 3.6 | 1.8 | 2.1 |
| 7 | 6.0 | 5.3 | 2.1 | 2.3 |
| 8 | 20.4 | 0.3 | 0.4 | 1.2 |
| 9 | 17.8 | 0.6 | 0.7 | 1.4 |
| 10 | 15.6 | 1.1 | 0.9 | 1.7 |
| 11 | 4.0 | 6.0 | 2.2 | 2.5 |
In order to investigate the silicate process hides alkali content expanding admixture utilizing silicon tetrachloride as by-product to prepare provided by the invention to the expansion effect of pelt, protein-polysaccharide removal effect, alkali content expanding admixture prepared by the above embodiment of random selecting of the present invention, be applied in pelt alkali swelling operation, its consumption is 6% of pelt quality, and increase weight according to pelt, thicken method of testing, Anthrone-sulfuricacid method determines pelt after the swelling agent expansion process of different amounts, expansion pelt thicken rate, proteoglycan content in rate of body weight gain and waste liquid, expansion waste liquid chemical oxygen demand (COD) (COD), waste liquid total solids level (TS), and test result and conventional lime liming are compared (see table 2).Result display is after alkali content expanding admixture process provided by the invention, and the rate that thickens of pelt, rate of body weight gain and protein-polysaccharide remove effect and conventional lime liming quite, and alkali swelling waste liquid COD, TS are significantly less than conventional lime liming.
Table 2
| Thicken rate (%) | Rate of body weight gain (%) | Expansion waste liquid proteoglycan content (mg/l) | Expansion waste liquid COD(mg/l) | Expansion waste liquid TS(mg/l) | |
| Process hides alkali content expanding admixture of the present invention | 98.23 | 32.90 | 123.28 | 1974 | 2241 |
| Conventional liming agent | 90.60 | 28.40 | 110.72 | 2187 | 3068 |
Claims (4)
1. the silicate process hides alkali content expanding admixture utilizing silicon tetrachloride as by-product to prepare, it is characterized in that single silicic acid that this process hides alkali content expanding admixture contains accounts for silicic acid total amount 4.0-21.0%, its molecular structure is
,
Two silicic acid account for silicic acid total amount 0.1-6.0%, and its molecular structure is
,
Three silicic acid account for silicic acid total amount 0.2-2.2%, and its molecular structure is
,
Modulus is 1.0-2.5, and this process hides alkali content expanding admixture is prepared from by following steps:
(1) preparation of silicic acid
100-300 part water is added in reactor, in reactor, silicon tetrachloride as by-product 60-180 part is added in 1-5 minute, abundant stirring makes it mix, ice bath is utilized to control reactor temperature to 20-70 DEG C, collect the hydrogen chloride gas reacting and discharge, and namely abundant stirring after 5-20 minute obtain silicic acid after silicic acid gel is formed simultaneously;
(2) preparation of disacidify silicic acid
Being transferred to by step (1) gained silicic acid gel can in temperature reaction device, and raise temperature of reactor to 70-130 DEG C, heated and stirred, reclaims hydrogen chloride gas simultaneously, namely obtains disacidify silicic acid after heated and stirred 2.0-12.0 hour;
(3) preparation of process hides alkali content expanding admixture
Get step (2) gained disacidify silicic acid 100-150 part, add water 10-30 part, basifier 20-50 part, alkalinisation treatment 0.5-2.0 hour at 20-40 DEG C, obtain silicate process hides alkali content expanding admixture,
Above material number used is mass fraction.
2., according to the silicate process hides alkali content expanding admixture described in claim 1, it is characterized in that this silicate contained by silicate process hides alkali content expanding admixture is water glass or potassium silicate.
3. silicate process hides alkali content expanding admixture according to claim 1, the silicon tetrachloride as by-product that it is characterized in that using in silicic acid preparation process is production of polysilicon silicon tetrachloride as by-product, trichlorosilane produces by product four chlorination
Silicon or methyl chlorosilane produce in silicon tetrachloride as by-product any one.
4. silicate process hides alkali content expanding admixture according to claim 1, the basifier that it is characterized in that using in alkalinization is sodium hydroxide, any one in potassium hydroxide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386415A (en) * | 2008-10-21 | 2009-03-18 | 魏昭荣 | Method for preparing inorganic chemical product using waste produced by polycrystalline silicon |
| KR20090061319A (en) * | 2007-12-11 | 2009-06-16 | 윤귀호 | Method for producing leather absorbed loess red ochre and for folkpercussion |
| CN101693524A (en) * | 2009-09-18 | 2010-04-14 | 邵家蓉 | Low-temperature treatment process of silicon tetrachloride |
| JP2012001693A (en) * | 2010-06-21 | 2012-01-05 | Seiren Co Ltd | Natural leather product excellent in oleic acid-proof nature |
-
2013
- 2013-07-11 CN CN201310290011.3A patent/CN103320549B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090061319A (en) * | 2007-12-11 | 2009-06-16 | 윤귀호 | Method for producing leather absorbed loess red ochre and for folkpercussion |
| CN101386415A (en) * | 2008-10-21 | 2009-03-18 | 魏昭荣 | Method for preparing inorganic chemical product using waste produced by polycrystalline silicon |
| CN101693524A (en) * | 2009-09-18 | 2010-04-14 | 邵家蓉 | Low-temperature treatment process of silicon tetrachloride |
| JP2012001693A (en) * | 2010-06-21 | 2012-01-05 | Seiren Co Ltd | Natural leather product excellent in oleic acid-proof nature |
Non-Patent Citations (2)
| Title |
|---|
| 无机盐复合物对生皮膨胀效果的研究;陈慧等;《中国皮革》;20120603;第41卷(第11期);第33页左栏和中间栏第1段、右栏第2段 * |
| 硅酸钠在造纸工业中的应用潜力分析;夏安军等;《黑龙江造纸》;20080305(第01期);第24页表2和左栏倒数第1段 * |
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