CN106281041A - The deodorization of a kind of crude sulfate turpentine and the production method of sulfate turpentine - Google Patents
The deodorization of a kind of crude sulfate turpentine and the production method of sulfate turpentine Download PDFInfo
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- CN106281041A CN106281041A CN201610694396.3A CN201610694396A CN106281041A CN 106281041 A CN106281041 A CN 106281041A CN 201610694396 A CN201610694396 A CN 201610694396A CN 106281041 A CN106281041 A CN 106281041A
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- sulfate turpentine
- washing
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- time
- crude sulfate
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 156
- 241000779819 Syncarpia glomulifera Species 0.000 title claims abstract description 144
- 239000001739 pinus spp. Substances 0.000 title claims abstract description 144
- 229940036248 turpentine Drugs 0.000 title claims abstract description 144
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000004332 deodorization Methods 0.000 title abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 105
- 239000007800 oxidant agent Substances 0.000 claims abstract description 50
- 230000001590 oxidative effect Effects 0.000 claims abstract description 50
- 238000013517 stratification Methods 0.000 claims abstract description 44
- 239000003513 alkali Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 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 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000002351 wastewater Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 16
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 15
- 230000001877 deodorizing effect Effects 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000005194 fractionation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 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
- 239000002253 acid 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
- 239000003463 adsorbent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 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
- 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
- XJBOZKOSICCONT-UHFFFAOYSA-N 4,6,6-trimethylbicyclo[3.1.1]hept-2-ene Chemical compound CC1C=CC2C(C)(C)C1C2 XJBOZKOSICCONT-UHFFFAOYSA-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
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011344 liquid material Substances 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
- 239000000376 reactant Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- -1 terpenoid hydroperoxides Chemical class 0.000 description 1
- 238000005303 weighing Methods 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
The deodorization of a kind of crude sulfate turpentine and the production method of sulfate turpentine, comprise the following steps: crude sulfate turpentine washing for the first time；Add oxidant and carry out oxidation reaction, control reaction temperature less than 70 DEG C, after oxidant adds, continue stirring reaction more than 2 hours, total addition of oxidant is 5wt%～10wt% of crude sulfate turpentine after for the first time washing, and described oxidant is that 50wt% hydrogen peroxide and concentrated sulphuric acid are in mass ratio for the mixture of 95:5～10；After completion of the reaction, stratification, collect upper strata crude sulfate turpentine；Second time washing, stratification, collect upper strata crude sulfate turpentine；The sodium hydrate aqueous solution adding 10v%～20v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, and the concentration of sodium hydrate aqueous solution is 5wt%～15wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine；Third time washing, stratification after washing, collect upper strata crude sulfate turpentine.
Description
Technical field
The present invention relates to the deodorizing method of by-product crude sulfate turpentine, the present invention in a kind of pulping and paper-making production process
Further relate to the production method of a kind of sulfate turpentine.
Background technology
Crude sulfate turpentine is the by-product produced in the sulfate pulping process with Masson Pine as raw material, Qi Zhongzhu
Wanting composition is australene and nopinene, is to obtain after the condensed cooling of the gas such as terpenoid substance, sulfide and oil-water separation
Yellow or dark red oil liquid.Containing cacodorous sulfur-containing compound in crude sulfate turpentine, but owing to its cost is relatively low
Honest and clean, gradually come into one's own, particularly produce because the raising of resin tapping cost, ecological environmental protection require higher at traditional gum turpentine
And in the case of being severely impacted, the production of people's pay attention to day by day sulfate turpentine.But owing to crude sulfate turpentine has
There is the deep gentle defect such as highly seasoned of color, it is impossible to substitute gum turpentine and use, typically cannot be directly used to the exploitation of downstream product.And
Sulfate turpentine after deodorization, decolorizing and refining process can be as artificial camphor, Borneolum Syntheticum, terpenic oil, terpenoid spice
And the raw material of the Oleum Terebinthinae derived product such as terpene resin, also can be directly used as gasoline additive etc. simultaneously, 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 is that modified activated carbon sieves mixture with water molecules.After preliminary oxidation
Washing separates, then by adsorbent, removes pungent odour, can contain by organic sulfur in efficient removal crude sulfate turpentine
Amount so that it is reach total sulfur content and meet the 10ppm standard required by further commercial Application.
CN101654597 discloses a kind of refining method for desulphurizing and deodorizing crude sulphate turpentine, terpenoid hydroperoxides
Add in reaction bulb together with oxidation deodorizing agent and sulfur-bearing, sulfate turpentine with foul smell, add at 50～150 DEG C
Thermal agitation reaction 4～20h, oxidation deodorizing agent addition in the reaction is the 1%～20% of raw material sulphuric acid salt Oleum Terebinthinae quality,
Adding distilled water wash reactant liquor, separatory removes water layer, and organic layer is again through vapor distillation, distillating of Fractional Collections different boiling
Liquid；Measure with microcomputer sulfur chlorine analyzers and respectively distillate the sulfur content in component, still liquid and raw material, i.e. obtain sulfur content≤20mg/l
Almost without foul smell, colourless POV salt Oleum Terebinthinae.Technical scheme disclosed in this patent, uses terpenoid hydroperoxidation
Thing production cost is higher,
In above technical method, exist and such as operate the weak points such as loaded down with trivial details, processing cost is high, refining effect is poor, but also
Exist and make the possibility that product is secondarily contaminated, as inevitably generated organic chloride when utilizing oxidation sweetening deodorize
Sulfate turpentine product is made to be secondarily contaminated.
Summary of the invention
For the deficiencies in the prior art, the technical problem to be solved is to provide a kind of crude sulfate turpentine
Deodorizing method and the production method of sulfate turpentine.
In order to solve above-mentioned technical problem, on the one hand, the present invention provides the deodorizing method of a kind of crude sulfate turpentine, bag
Include following steps:
Crude sulfate turpentine mixes with water and carries out washing for the first time, and stratification after washing collects upper strata crude sulphate Lignum Pini Nodi
Oil, discharges bottom waste water；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
5wt%～10wt%, the mixture that described oxidant is 50wt% hydrogen peroxide and concentrated sulphuric acid is 95:5～10 in mass ratio, or other
The H of concentration hydrogen peroxide equivalent2O2Addition；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；
The sodium hydrate aqueous solution adding 10v%～20v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, institute
The concentration stating sodium hydrate aqueous solution is 5wt%～15wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine, will
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water.
As improving technical scheme further, the deodorizing method of the crude sulfate turpentine that the present invention provides, described alkali cleaning
Temperature is 45～55 DEG C.
As improving technical scheme further, the deodorizing method of the crude sulfate turpentine that the present invention provides, described first
The water consumption of secondary washing, second time washing and third time washing is 20v%～40v% of crude sulfate turpentine.
In order to solve above-mentioned technical problem, on the other hand, the present invention provides the production method of a kind of sulfate turpentine, bag
Include following steps:
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
Described crude sulfate turpentine mixes with water and carries out washing for the first time, and stratification after washing collects upper strata crude sulphate
Oleum Terebinthinae, discharges bottom waste water；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
5wt%～10wt%, the mixture that described oxidant is 50wt% hydrogen peroxide and concentrated sulphuric acid is 95:5～10 in mass ratio, or other
The H of concentration hydrogen peroxide equivalent2O2Addition；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；
The sodium hydrate aqueous solution adding 10v%～20v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, institute
The concentration stating sodium hydrate aqueous solution is 5wt%～15wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine, will
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water.
Being distilled by crude sulfate turpentine after third time washing, fraction during collection 110 DEG C respectively, when 140 DEG C
Fraction and distillation clout, prepare corresponding product.
As improving technical scheme further, the production method of the sulfate turpentine that the present invention provides, described alkali cleaning temperature
Degree is 45～55 DEG C.
As improving technical scheme further, the production method of the sulfate turpentine that the present invention provides, described first time
The water consumption of washing, second time washing 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 operation, the former production process of process is more, there occurs a series of crosslinking and isomerization
Reaction, more complicated than the component of the latter, color is deeper, and stink is heavier.
Organosulfur compound in the technical scheme energy efficient removal crude sulfate turpentine that the present invention provides, deodorizing effect is bright
Aobvious, there is good decolorizing effect simultaneously.It is especially suitable for weighing, to from evaporation station, the crude sulphate Lignum Pini Nodi collected in foul condensate
Oil carries out deodorization and decolouring.
Detailed description of the invention
Embodiment is used for providing a further understanding of the present invention, constitutes the part of the application, and the present invention's is schematic
Embodiment and explanation thereof are used for explaining the present invention, are not intended that inappropriate limitation 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 collected mix with water and carries out first time and wash, stratification after washing, collection upper strata thick sulphuric acid
Salt Oleum Terebinthinae, discharges bottom waste water；In this step, washing water consumption is the 20v% of this step crude sulfate turpentine for the first time；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
5wt%, the mixture that described oxidant is 50wt% hydrogen peroxide and sulphuric acid is 95:5 in mass ratio；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；In this step, second time washing water consumption is the 20v% of this step crude sulfate turpentine；
The sodium hydrate aqueous solution adding 10v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, alkali cleaning temperature
Being 55 DEG C, the concentration of described sodium hydrate aqueous solution is 15wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine,
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water；In this step, second time washing water consumption is this step crude sulfate turpentine
40v%；
Crude sulfate turpentine after third time washing is distilled, fraction during collection 110 DEG C, evaporating when 140 DEG C respectively
Divide and distillation clout, prepare corresponding product.
Embodiment 2
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine collected mix with water and carries out first time and wash, stratification after washing, collection upper strata thick sulphuric acid
Salt Oleum Terebinthinae, discharges bottom waste water；In this step, washing water consumption is the 40v% of this step crude sulfate turpentine for the first time；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
10wt%, the mixture that described oxidant is 50wt% hydrogen peroxide and sulphuric acid is 95:10 in mass ratio；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；In this step, second time washing water consumption is the 40v% of this step crude sulfate turpentine；
The sodium hydrate aqueous solution adding 20v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, alkali cleaning temperature
Being 45 DEG C, the concentration of described sodium hydrate aqueous solution is 5wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine,
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water；In this step, second time washing water consumption is this step crude sulfate turpentine
20v%；
Crude sulfate turpentine after third time washing is distilled, fraction during collection 110 DEG C, evaporating when 140 DEG C respectively
Divide and distillation clout, prepare corresponding product.
Embodiment 3
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine collected mix with water and carries out first time and wash, stratification after washing, collection upper strata thick sulphuric acid
Salt Oleum Terebinthinae, discharges bottom waste water；In this step, washing water consumption is the 30v% of this step crude sulfate turpentine for the first time；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
8wt%, the mixture that described oxidant is 50wt% hydrogen peroxide and sulphuric acid is 95:7 in mass ratio；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；In this step, second time washing water consumption is the 32v% of this step crude sulfate turpentine；
The sodium hydrate aqueous solution adding 15v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, alkali cleaning temperature
Being 50 DEG C, the concentration of described sodium hydrate aqueous solution is 10wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine,
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water；In this step, second time washing water consumption is this step crude sulfate turpentine
28v%；
Crude sulfate turpentine after third time washing is distilled, fraction during collection 110 DEG C, evaporating when 140 DEG C respectively
Divide and distillation clout, prepare corresponding product.
Embodiment 4
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
The crude sulfate turpentine collected mix with water and carries out first time and wash, stratification after washing, collection upper strata thick sulphuric acid
Salt Oleum Terebinthinae, discharges bottom waste water；In this step, washing water consumption is the 30v% of this step crude sulfate turpentine for the first time；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
8wt%, the mixture that described oxidant is 30wt% hydrogen peroxide and sulphuric acid is 162:7 in mass ratio；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；In this step, second time washing water consumption is the 32v% of this step crude sulfate turpentine；
The sodium hydrate aqueous solution adding 15v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, alkali cleaning temperature
Being 50 DEG C, the concentration of described sodium hydrate aqueous solution is 10wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine,
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water；In this step, second time washing water consumption is this step crude sulfate turpentine
28v%；
Crude sulfate turpentine after third time washing is distilled, fraction during collection 110 DEG C, evaporating when 140 DEG C respectively
Divide and distillation clout, prepare corresponding product.
Comparative example 1, not sulfur acid in oxidant on the basis of embodiment 1.
Comparative example 2, not sulfur acid in oxidant on the basis of embodiment 2.
Comparative example 3, not sulfur acid in oxidant on the basis of embodiment 2.
Comparative example 4, on the basis of embodiment 1, do not use hydrogen peroxide in oxidant.Its product does not reaches deodorize and takes off
The technique effect of sulfur.
Above example and the product of comparative example's gained, with gas chromatography, by GB/T 12902-2006 Lignum Pini Nodi
Oil analysis method, detects relevant index, testing result such as following table:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Pinene 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 |
Use anvil tintometer, the product of above example and comparative example's gained is carried out colorimetric, measures the face of products obtained therefrom
Color.Wherein the color of embodiment 1～4 products obtained therefrom is No. 2 colors, and the color of comparative example's products obtained therefrom is No. 4 colors.
More than test explanation: at the H using equivalent2O2Under premise, the content of hydrogen peroxide in oxidant, the quality to product
Affect inconspicuous.Adding sulphuric acid, the sulfur content of products obtained therefrom is lower, and color is more shallow, uses more merely H2O2Technique effect more
Excellent.
For a person skilled in the art, the present invention can have various modifications and variations.All right of the present invention want
Within the spirit asked and principle, any modification, equivalent substitution and improvement etc. made, should be included in protection scope of the present invention
Within.
Claims (7)
1. the deodorizing method of a crude sulfate turpentine, it is characterised in that comprise the following steps:
Crude sulfate turpentine mixes with water and carries out washing for the first time, and stratification after washing collects upper strata crude sulphate Lignum Pini Nodi
Oil, discharges bottom waste water；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
5wt%～10wt%, the mixture that described oxidant is 50wt% hydrogen peroxide and concentrated sulphuric acid is 95:5～10 in mass ratio, or other
The H of concentration hydrogen peroxide equivalent2O2Addition；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；
The sodium hydrate aqueous solution adding 10v%～20v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, institute
The concentration stating sodium hydrate aqueous solution is 5wt%～15wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine, will
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water.
The deodorizing method of crude sulfate turpentine the most according to claim 1, it is characterised in that described alkali cleaning temperature is 45
～55 DEG C.
The deodorizing method of crude sulfate turpentine the most according to claim 1, it is characterised in that the washing of described first time,
The water consumption of second time washing and third time washing is 20v%～40v% of crude sulfate turpentine.
4. the production method of a sulfate turpentine, it is characterised in that comprise the following steps:
Crude sulfate turpentine is collected in the heavy foul condensate at slurrying alkali collection evaporation station；
Described crude sulfate turpentine mixes with water and carries out washing for the first time, and stratification after washing collects upper strata crude sulphate
Oleum Terebinthinae, discharges bottom waste water；
Under agitation, carry out toward the crude sulfate turpentine after for the first time washing adds oxidant continuously or in batches
Oxidation reaction, controls the addition speed of oxidant according to reaction temperature, controls reaction temperature and is less than 70 DEG C, and oxidant adds
After, continue stirring reaction more than 2 hours；Total addition of described oxidant is crude sulfate turpentine after washing for the first time
5wt%～10wt%, the mixture that described oxidant is 50wt% hydrogen peroxide and concentrated sulphuric acid is 95:5～10 in mass ratio, or other
The H of concentration hydrogen peroxide equivalent2O2Addition；
After completion of the reaction, stratification, collect upper strata crude sulfate turpentine, bottom waste water is discharged；Toward crude sulphate Lignum Pini Nodi
Oil adds water carry out washing for the second time, stratification after washing, collect upper strata crude sulfate turpentine, bottom waste water is arranged
Go out；
The sodium hydrate aqueous solution adding 10v%～20v% in the crude sulfate turpentine after second time washing carries out alkali cleaning, institute
The concentration stating sodium hydrate aqueous solution is 5wt%～15wt%；Stratification after alkali cleaning, collects upper strata crude sulfate turpentine, will
Bottom waste water is discharged；
In the crude sulfate turpentine after alkali cleaning, add water carry out washing for the third time, stratification after washing, collect upper strata thick
Sulfate turpentine, discharges bottom waste water.
5. the crude sulfate turpentine after third time washing is distilled, fraction during collection 110 DEG C respectively, when 140 DEG C
Fraction and distillation clout, prepare corresponding product.
The production method of sulfate turpentine the most according to claim 4, it is characterised in that described alkali cleaning temperature be 45～
55℃。
The production method of sulfate turpentine the most according to claim 4, it is characterised in that washing of described first time, the
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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