CN106281041B - A kind of deodorization of crude sulfate turpentine and the production method of sulfate turpentine - Google Patents
A kind of deodorization of crude sulfate turpentine and the production method of sulfate turpentine Download PDFInfo
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- CN106281041B CN106281041B CN201610694396.3A CN201610694396A CN106281041B CN 106281041 B CN106281041 B CN 106281041B CN 201610694396 A CN201610694396 A CN 201610694396A CN 106281041 B CN106281041 B CN 106281041B
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- sulfate turpentine
- turpentine
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 158
- 241000779819 Syncarpia glomulifera Species 0.000 title claims abstract description 149
- 239000001739 pinus spp. Substances 0.000 title claims abstract description 148
- 229940036248 turpentine Drugs 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000004332 deodorization Methods 0.000 title abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 52
- 230000001590 oxidative effect Effects 0.000 claims abstract description 52
- 238000013517 stratification Methods 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 42
- 239000003513 alkali Substances 0.000 claims abstract description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000004140 cleaning Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000002351 wastewater Substances 0.000 claims description 40
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- 239000001293 FEMA 3089 Substances 0.000 claims description 13
- 230000001877 deodorizing effect Effects 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- HYJODZUSLXOFNC-UHFFFAOYSA-N [S].[Cl] Chemical compound [S].[Cl] HYJODZUSLXOFNC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- -1 terpene hydroperoxides Chemical class 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F3/00—Obtaining spirits of turpentine
- C09F3/02—Obtaining spirits of turpentine as a by-product in the paper-pulping process
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F3/00—Obtaining spirits of turpentine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of deodorization of crude sulfate turpentine and the production method of sulfate turpentine, comprising the following steps: crude sulfate turpentine first wash；Oxidant is added and carries out oxidation reaction, it controls reaction temperature and is no more than 70 DEG C, after oxidant adds, continue to be stirred to react 2 hours or more, total additional amount of oxidant is 5wt%~10wt% of crude sulfate turpentine after first wash, and the oxidant is 50wt% hydrogen peroxide and the concentrated sulfuric acid is the mixture of 95:5~10 in mass ratio；After completion of the reaction, stratification collects upper layer crude sulfate turpentine；Second wash, stratification collect upper layer crude sulfate turpentine；The sodium hydrate aqueous solution that 10v%~20v% is added into the crude sulfate turpentine after second wash carries out alkali cleaning, and the concentration of sodium hydrate aqueous solution is 5wt%~15wt%；Stratification after alkali cleaning collects upper layer crude sulfate turpentine；Third time is washed, stratification after washing, collects upper layer crude sulfate turpentine.
Description
Technical field
The present invention relates to a kind of deodorizing methods of by-product crude sulfate turpentine in pulping and paper-making production process, the present invention
Further relate to a kind of production method of sulfate turpentine.
Background technique
Crude sulfate turpentine is the by-product generated in the sulfate pulping process using pine as raw material, wherein leading
Wanting ingredient is australene and nopinene, is that the gases such as terpenoid substance, sulfide obtain after condensation cooling and water-oil separating
Yellow or dark red oil liquid.Containing the sulfur-containing compound of foul smelling in crude sulfate turpentine, but since its cost is relatively low
It is honest and clean, it is gradually taken seriously, especially in traditional gum turpentine production because the raising of resin tapping cost, ecological environmental protection requirement are higher
And in the case where being severely impacted, the production of people's pay attention to day by day sulfate turpentine.But since crude sulfate turpentine has
There is the defects of color is deeply gentle highly seasoned, gum turpentine use can not be substituted, generally cannot be directly used to the exploitation of downstream product.And
By deodorization, decolorizing and refining, treated that sulfate turpentine can be used as artificial camphor, borneol, terpenic oil, terpene fragrance
And the raw material of the turpentine oil derived product such as terpene resin, while gasoline additive can also be directly used as etc., there is wide city
Field prospect.
CN104449395A discloses a kind of refining method for desulphurizing and deodorizing crude sulphate turpentine, and oxidant is effective chlorine
The liquor natrii hypochloritis of content 3%-10%, adsorbent are that modified activated carbon and water molecules sieve mixture.After preliminary oxidation
Washing separation, then adsorbed by adsorbent, pungent odour is removed, organic sulfur can be contained in efficient removal crude sulfate turpentine
Amount, reaches total sulfur content and meets 10ppm standard required by further industrial application.
CN101654597 discloses a kind of refining method for desulphurizing and deodorizing crude sulphate turpentine, terpene hydroperoxides
It is added in reaction flask together with sulfur-bearing, the sulfate turpentine with foul smell as oxidation deodorizing agent, adds at 50~150 DEG C
4~20h is reacted in thermal agitation, and the additional amount of oxidation deodorizing agent in the reaction is the 1%~20% of raw material sulphuric acid salt turpentine oil quality,
Add distilled water washing reaction liquid, liquid separation removes water layer, and organic layer is distillated using steam distillation, Fractional Collections different boiling
Liquid；The sulfur content in component, kettle liquid and raw material is respectively distillated with the measurement of microcomputer sulphur chlorine analyzers to get sulfur content≤20mg/l is arrived
Almost without foul smell, colourless refined sulfuric acid salt turpentine oil.The technical solution of the patent disclosure uses terpene hydroperoxidation
Object production cost is higher,
In above technical method, exist in place of such as operating the deficiencies of loaded down with trivial details, processing cost is high, refining effect is poor, and
And there is also the possibility for being secondarily contaminated product, inevitably generate organic chloride when being such as deodorized using oxidation sweetening
Object and be secondarily contaminated sulfate turpentine product.
Summary of the invention
In view of the deficiencies of the prior art, technical problem to be solved by the invention is to provide a kind of crude sulfate turpentines
The production method of deodorizing methods and sulfate turpentine.
In order to solve the above-mentioned technical problem, on the one hand, the present invention provides a kind of deodorizing methods of crude sulfate turpentine, packet
Include following steps:
Crude sulfate turpentine is mixed with water carries out first wash, and stratification after washing collects upper layer crude sulphate
Bottom waste water is discharged turpentine oil；
Under agitation, continuous into the crude sulfate turpentine after first wash or oxidant is added in batches
Oxidation reaction is carried out, the addition speed of oxidant is controlled according to reaction temperature, control reaction temperature is no more than 70 DEG C, and oxidant adds
After complete, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
5wt%~10wt%, the oxidant is 50wt% hydrogen peroxide and the concentrated sulfuric acid is the mixture or other of 95:5~10 in mass ratio
The H of concentration hydrogen peroxide equivalent2O2Additional amount；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate
Water is added in turpentine oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, by bottom waste water
Discharge；
The sodium hydrate aqueous solution that 10v%~20v% is added into the crude sulfate turpentine after second wash carries out alkali
It washes, the concentration of the sodium hydrate aqueous solution is 5wt%~15wt%；Stratification after alkali cleaning collects upper layer crude sulphate turpentine
Bottom waste water is discharged oil；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, stratification after washing, in collection
Layer crude sulfate turpentine, bottom waste water is discharged.
As further improvement technical solution, the deodorizing methods of crude sulfate turpentine provided by the invention, the alkali cleaning
Temperature is 45~55 DEG C.
As be further improved technical solution, the deodorizing methods of crude sulfate turpentine provided by the invention, described first
The water consumption of secondary washing, second wash and third time washing is 20v%~40v% of crude sulfate turpentine.
In order to solve the above-mentioned technical problem, on the other hand, the present invention provides a kind of production method of sulfate turpentine, wraps
Include following steps:
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine is mixed with water carries out first wash, and stratification after washing collects the thick sulphur in upper layer
Bottom waste water is discharged hydrochlorate turpentine oil；
Under agitation, continuous into the crude sulfate turpentine after first wash or oxidant is added in batches
Oxidation reaction is carried out, the addition speed of oxidant is controlled according to reaction temperature, control reaction temperature is no more than 70 DEG C, and oxidant adds
After complete, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
5wt%~10wt%, the oxidant is 50wt% hydrogen peroxide and the concentrated sulfuric acid is the mixture or other of 95:5~10 in mass ratio
The H of concentration hydrogen peroxide equivalent2O2Additional amount；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate
Water is added in turpentine oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, by bottom waste water
Discharge；
The sodium hydrate aqueous solution that 10v%~20v% is added into the crude sulfate turpentine after second wash carries out alkali
It washes, the concentration of the sodium hydrate aqueous solution is 5wt%~15wt%；Stratification after alkali cleaning collects upper layer crude sulphate turpentine
Bottom waste water is discharged oil；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, stratification after washing, in collection
Layer crude sulfate turpentine, bottom waste water is discharged.
Crude sulfate turpentine after third time is washed distills, fraction when collecting 110 DEG C respectively, at 140 DEG C
Fraction and distillation clout, corresponding product is made.
As further improvement technical solution, the production method of sulfate turpentine provided by the invention, the alkali cleaning temperature
Degree is 45~55 DEG C.
As further improvement technical solution, the production method of sulfate turpentine provided by the invention, the first time
The water consumption of washing, second wash and third time washing is 20v%~40v% of crude sulfate turpentine.
The crude sulfate turpentine collected in the heavy foul condensate at slurrying alkali collection evaporation station, is different from from pulping and digesting
The crude sulfate turpentine collected in process, the production process that the former passes through is more, and a series of crosslinking and isomerization has occurred
Reaction, more complicated than the component of the latter, darker, stink is heavier.
Organosulfur compound in technical solution energy efficient removal crude sulfate turpentine provided by the invention, deodorizing effect are bright
It is aobvious, while there is good decolorizing effect.It is especially suitable for the crude sulphate turpentine collected from the heavy foul condensate at evaporation station
Oil carries out deodorization and decoloration.
Specific embodiment
Embodiment is used to provide further understanding of the present invention, and is constituted part of this application, and of the invention is schematic
Examples and descriptions thereof are used to explain the present invention, does not constitute improper limitations of the present invention.
Embodiment 1
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine of collection is mixed with water carries out first wash, and it is thick to collect upper layer for stratification after washing
Bottom waste water is discharged sulfate turpentine；First wash water consumption is this step crude sulfate turpentine in this step
20v%；
Under agitation, continuous into the crude sulfate turpentine after first wash or oxidant is added in batches
Oxidation reaction is carried out, the addition speed of oxidant is controlled according to reaction temperature, control reaction temperature is no more than 70 DEG C, and oxidant adds
After complete, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
5wt%, the oxidant are the mixture that 50wt% hydrogen peroxide and sulfuric acid are 95:5 in mass ratio；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate
Water is added in turpentine oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, by bottom waste water
Discharge；Second wash water consumption is the 20v% of this step crude sulfate turpentine in this step；
The sodium hydrate aqueous solution that 10v% is added into the crude sulfate turpentine after second wash carries out alkali cleaning, alkali cleaning
Temperature is 55 DEG C, and the concentration of the sodium hydrate aqueous solution is 15wt%；Stratification after alkali cleaning collects upper layer crude sulphate pine
Bottom waste water is discharged for fuel-economizing；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, stratification after washing, in collection
Layer crude sulfate turpentine, bottom waste water is discharged；Second wash water consumption is this step crude sulphate turpentine in this step
The 40v% of oil；
Crude sulfate turpentine after third time is washed distills, fraction when collecting 110 DEG C respectively, at 140 DEG C
Fraction and distillation clout, corresponding product is made.
Embodiment 2
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine of collection is mixed with water carries out first wash, and it is thick to collect upper layer for stratification after washing
Bottom waste water is discharged sulfate turpentine；First wash water consumption is this step crude sulfate turpentine in this step
40v%；
Under agitation, continuous into the crude sulfate turpentine after first wash or oxidant is added in batches
Oxidation reaction is carried out, the addition speed of oxidant is controlled according to reaction temperature, control reaction temperature is no more than 70 DEG C, and oxidant adds
After complete, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
10wt%, the oxidant are the mixture that 50wt% hydrogen peroxide and sulfuric acid are 95:10 in mass ratio；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate
Water is added in turpentine oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, by bottom waste water
Discharge；Second wash water consumption is the 40v% of this step crude sulfate turpentine in this step；
The sodium hydrate aqueous solution that 20v% is added into the crude sulfate turpentine after second wash carries out alkali cleaning, alkali cleaning
Temperature is 45 DEG C, and the concentration of the sodium hydrate aqueous solution is 5wt%；Stratification after alkali cleaning collects upper layer crude sulphate turpentine
Bottom waste water is discharged oil；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, stratification after washing, in collection
Layer crude sulfate turpentine, bottom waste water is discharged；Second wash water consumption is this step crude sulphate turpentine in this step
The 20v% of oil；
Crude sulfate turpentine after third time is washed distills, fraction when collecting 110 DEG C respectively, at 140 DEG C
Fraction and distillation clout, corresponding product is made.
Embodiment 3
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine of collection is mixed with water carries out first wash, and it is thick to collect upper layer for stratification after washing
Bottom waste water is discharged sulfate turpentine；First wash water consumption is this step crude sulfate turpentine in this step
30v%；
Under agitation, continuous into the crude sulfate turpentine after first wash or oxidant is added in batches
Oxidation reaction is carried out, the addition speed of oxidant is controlled according to reaction temperature, control reaction temperature is no more than 70 DEG C, and oxidant adds
After complete, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
8wt%, the oxidant are the mixture that 50wt% hydrogen peroxide and sulfuric acid are 95:7 in mass ratio；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate
Water is added in turpentine oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, by bottom waste water
Discharge；Second wash water consumption is the 32v% of this step crude sulfate turpentine in this step；
The sodium hydrate aqueous solution that 15v% is added into the crude sulfate turpentine after second wash carries out alkali cleaning, alkali cleaning
Temperature is 50 DEG C, and the concentration of the sodium hydrate aqueous solution is 10wt%；Stratification after alkali cleaning collects upper layer crude sulphate pine
Bottom waste water is discharged for fuel-economizing；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, stratification after washing, in collection
Layer crude sulfate turpentine, bottom waste water is discharged；Second wash water consumption is this step crude sulphate turpentine in this step
The 28v% of oil；
Crude sulfate turpentine after third time is washed distills, fraction when collecting 110 DEG C respectively, at 140 DEG C
Fraction and distillation clout, corresponding product is made.
Embodiment 4
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine of collection is mixed with water carries out first wash, and it is thick to collect upper layer for stratification after washing
Bottom waste water is discharged sulfate turpentine；First wash water consumption is this step crude sulfate turpentine in this step
30v%；
Under agitation, continuous into the crude sulfate turpentine after first wash or oxidant is added in batches
Oxidation reaction is carried out, the addition speed of oxidant is controlled according to reaction temperature, control reaction temperature is no more than 70 DEG C, and oxidant adds
After complete, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
8wt%, the oxidant are the mixture that 30wt% hydrogen peroxide and sulfuric acid are 162:7 in mass ratio；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate
Water is added in turpentine oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, by bottom waste water
Discharge；Second wash water consumption is the 32v% of this step crude sulfate turpentine in this step；
The sodium hydrate aqueous solution that 15v% is added into the crude sulfate turpentine after second wash carries out alkali cleaning, alkali cleaning
Temperature is 50 DEG C, and the concentration of the sodium hydrate aqueous solution is 10wt%；Stratification after alkali cleaning collects upper layer crude sulphate pine
Bottom waste water is discharged for fuel-economizing；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, stratification after washing, in collection
Layer crude sulfate turpentine, bottom waste water is discharged；Second wash water consumption is this step crude sulphate turpentine in this step
The 28v% of oil；
Crude sulfate turpentine after third time is washed distills, fraction when collecting 110 DEG C respectively, at 140 DEG C
Fraction and distillation clout, corresponding product is made.
Comparative example 1, on the basis of embodiment 1 not sulfur acid in oxidant.
Comparative example 2, the not sulfur acid in oxidant on the basis of embodiment 2.
Comparative example 3, the not sulfur acid in oxidant on the basis of embodiment 2.
Comparative example 4 does not use hydrogen peroxide on the basis of embodiment 1 in oxidant.It is de- that deodorization is not achieved in its product
The technical effect of sulphur.
Above embodiments and comparative example resulting product, with gas chromatography, by GB/T 12902-2006 turpentine
Oil analysis method detects relevant index, and testing result is as follows:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Firpene content wt% | 73.34 | 73.37 | 73.32 | 73.35 | 73.36 | 73.34 | 73.31 |
| Dipentene content wt% | 18.1 | 18.0 | 18.1 | 18.1 | 18.0 | 18.1 | 18.1 |
| Sulfide content wt% | 1.15 | 1.14 | 1.17 | 1.19 | 2.55 | 2.49 | 2.53 |
With anvil colorimeter, colorimetric is carried out to above embodiments and comparative example resulting product, measures products obtained therefrom
Color.Wherein the color of Examples 1 to 4 products obtained therefrom is No. 2 colors, and the color of comparative example products obtained therefrom is No. 4
Color.
The above test explanation: in the H using equivalent2O2Under the premise of, the content of hydrogen peroxide in oxidant, to the quality of product
It influences unobvious.Sulfuric acid is added, the sulfur content of products obtained therefrom is lower, and color is more shallow, relatively uses H merely2O2Technical effect more
It is excellent.
For those skilled in the art, the invention may be variously modified and varied.It is all to be wanted in right of the present invention
Within the spirit and principle asked, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (6)
1. a kind of deodorizing methods of crude sulfate turpentine, which comprises the following steps:
Crude sulfate turpentine is mixed with water carries out first wash, and stratification after washing collects upper layer crude sulphate turpentine
Bottom waste water is discharged oil；
Under agitation, continuous into the crude sulfate turpentine after first wash or addition oxidant progress in batches
Oxidation reaction controls the addition speed of oxidant according to reaction temperature, and control reaction temperature is no more than 70 DEG C, and oxidant adds
Afterwards, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
5wt%~10wt%, the oxidant is 50wt% hydrogen peroxide and the concentrated sulfuric acid is the mixture of 95:5~10, oxidant in mass ratio
In hydrogen peroxide used or be and 50wt% hydrogen peroxide equivalent H2O2Other concentration hydrogen peroxide；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate turpentine
Water is added in oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, bottom waste water is arranged
Out；
The sodium hydrate aqueous solution that 10v%~20v% is added into the crude sulfate turpentine after second wash carries out alkali cleaning, institute
The concentration for stating sodium hydrate aqueous solution is 5wt%~15wt%；Stratification after alkali cleaning collects upper layer crude sulfate turpentine, will
The discharge of bottom waste water；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, it is thick to collect upper layer for stratification after washing
Bottom waste water is discharged sulfate turpentine.
2. the deodorizing methods of crude sulfate turpentine according to claim 1, which is characterized in that the alkali cleaning temperature is 45
~55 DEG C.
3. the deodorizing methods of crude sulfate turpentine according to claim 1, which is characterized in that the first wash,
Second wash and the water consumption of third time washing are 20v%~40v% of crude sulfate turpentine.
4. a kind of production method of sulfate turpentine, which comprises the following steps:
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine is mixed with water carries out first wash, and stratification after washing collects upper layer crude sulphate
Bottom waste water is discharged turpentine oil；
Under agitation, continuous into the crude sulfate turpentine after first wash or addition oxidant progress in batches
Oxidation reaction controls the addition speed of oxidant according to reaction temperature, and control reaction temperature is no more than 70 DEG C, and oxidant adds
Afterwards, continue to be stirred to react 2 hours or more；Total additional amount of the oxidant is crude sulfate turpentine after first wash
5wt%~10wt%, the oxidant is 50wt% hydrogen peroxide and the concentrated sulfuric acid is the mixture of 95:5~10, oxidant in mass ratio
In hydrogen peroxide used or be and 50wt% hydrogen peroxide equivalent H2O2Other concentration hydrogen peroxide；
After completion of the reaction, stratification collects upper layer crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate turpentine
Water is added in oil and carries out second wash, stratification after washing collects upper layer crude sulfate turpentine, bottom waste water is arranged
Out；
The sodium hydrate aqueous solution that 10v%~20v% is added into the crude sulfate turpentine after second wash carries out alkali cleaning, institute
The concentration for stating sodium hydrate aqueous solution is 5wt%~15wt%；Stratification after alkali cleaning collects upper layer crude sulfate turpentine, will
The discharge of bottom waste water；
Water is added into the crude sulfate turpentine after alkali cleaning and carries out third time washing, it is thick to collect upper layer for stratification after washing
Bottom waste water is discharged sulfate turpentine；
Crude sulfate turpentine after third time is washed distills, fraction when collecting 110 DEG C respectively, evaporating at 140 DEG C
Divide and distill clout, corresponding product is made.
5. the production method of sulfate turpentine according to claim 4, which is characterized in that the alkali cleaning temperature be 45~
55℃。
6. the production method of sulfate turpentine according to claim 4, which is characterized in that the first wash,
The water consumption of secondary washing and third time washing is 20v%~40v% of crude sulfate turpentine.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB239878A (en) * | 1924-09-12 | 1926-12-13 | Hoechst Ag | Process for improving decamphorated oil of turpentine |
| CN101654597A (en) * | 2009-09-04 | 2010-02-24 | 中国林业科学研究院林产化学工业研究所 | Refining method for desulphurizing and deodorizing crude sulphate turpentine |
| CN103787818A (en) * | 2014-03-06 | 2014-05-14 | 南京运华立太能源科技有限公司 | Refined method for crude sulfate turpentine |
| CN104449395A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | Desulfurization deordorization refining method of crude sulfate turpentine |
-
2016
- 2016-08-22 CN CN201610694396.3A patent/CN106281041B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB239878A (en) * | 1924-09-12 | 1926-12-13 | Hoechst Ag | Process for improving decamphorated oil of turpentine |
| CN101654597A (en) * | 2009-09-04 | 2010-02-24 | 中国林业科学研究院林产化学工业研究所 | Refining method for desulphurizing and deodorizing crude sulphate turpentine |
| CN104449395A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | Desulfurization deordorization refining method of crude sulfate turpentine |
| CN103787818A (en) * | 2014-03-06 | 2014-05-14 | 南京运华立太能源科技有限公司 | Refined method for crude sulfate turpentine |
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