CN103787818A - Refined method for crude sulfate turpentine - Google Patents
Refined method for crude sulfate turpentine Download PDFInfo
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- CN103787818A CN103787818A CN201410080213.XA CN201410080213A CN103787818A CN 103787818 A CN103787818 A CN 103787818A CN 201410080213 A CN201410080213 A CN 201410080213A CN 103787818 A CN103787818 A CN 103787818A
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Abstract
The invention relates to a refined method for crude sulfate turpentine. The method for the crude sulfate turpentine comprises the following steps that (1),CST conducted heat transfer enters a flashing tower to conduct flash separation, materials flowing from the bottom of the flashing tower are collected and sent to the middle portion of a vacuum rectifying column to be rectified and separated; (2), after materials flowing from the tower roof of the vacuum rectifying column are heat transferred, the materials enter an oxidation absorption tower to be oxidized and adsorbed; (3), materials after being oxidized and adsorbed enter an alkali wash reaction still and are alkali washed by alkaline solutions; (4), materials after being alkali washed enter a phase splitter, an upper layer oil phase acquired from layers being separated enters ithe vacuum rectifying column with a side line discharging to be separated, a Alpha-pinene product is acquired from an upper side line and a Beta -pinene product is acquired from a lower side line. The refined method for the crude sulfate turpentine applies a method which combines the processes of rectification, adsorption and chemical oxidation to acquire a pinene product with super low sulfur. The refined method for the crude sulfate turpentine is simple, low in energy consumption and production cost, and high in industrial reliability.
Description
Invention field
The present invention relates to turps, be specifically related to the terebinthine desulfurization of crude sulphate and purify, relate to more specifically the terebinthine super low sulfur firpene of a kind of crude sulphate product purification method.
Background technology
Turps is that one has bioactive natural product, and its main component is α-pinene and beta-pinene, has been widely used in the product development in the fields such as medicine, agricultural chemicals, resin, information industry, communication at present.
Different according to source, turps can be divided into four kinds of gum turpentines, crude sulphate turps (hereinafter to be referred as CST), steam-distilled(wood)turpentine, destructive distillation turpentine.China is mainly take gum turpentine as main.Because the resin tapping cost of gum turpentine is higher, the parent that the CST that therefore production cost is lower obtains more and more producers and consumers looks at.
CST is the by product of producing paper pulp take pine as raw material by sulphate process, and along with the increase of paper pulp demand, the output of CST will increase thereupon.Because CST contains a large amount of sulfurous organic compounds, color is dark, smell weight, can not be directly used in Downstream Products, need to pass through desulfuration purification, make it reach certain specification, use through the alternative gum turpentine of refining CST, as as products such as the synthetic Terpineol 350 of raw material, camphor, terpene resins, therefore, there are wide market outlook.
CST main component is terpenoid and sulfocompound, and terpenoid mainly contains α-pinene, beta-pinene and other monoterpene alkene on a small quantity, and total content is 85%-92%, and sulfocompound is mainly mercaptan, thioether, sulphur sulfone etc., and total content is 8%-15%.The refining of CST is mainly to its desulfurization, and more conventional process for purification has Physical, chemical method and treatment process that the two is combined with at present; Conventionally chemical method is combined to reach good refining effect with Physical.
(food and machinery, 2013,29 such as Chen Lei, 1) a kind of CST desulfurization refining method is disclosed, first after CST being utilized to NaOH washing, carry out wet distillation, use afterwards a certain amount of zinc oxide oxide treatment, finally utilize the turps after charcoal absorption is refined.
Chinese patent CN101654595A, a kind of method of CST desulfuration purification is disclosed, a certain amount of oxygenant terpene hydroperoxide are reacted with CST, wash afterwards layering with water, take out oil phase, the distillate of oil phase rectifying being collected to different boiling, obtains sulphur content lower than 20ppm and does not almost have cacodorous POV salt turps.But this method is not thorough to the oxidation of sulphur compound, be difficult to obtain the firpene product containing super low sulfur.
Chinese patent CN102796457A, a kind of CST process for purification is disclosed, first adopt special rectification under vacuum method to collect the cut of different boiling, recycling certain density chlorine bleach liquor is oxidized cut, stratification after product after oxidation adds a certain proportion of water to wash 2-3 time again, remove water, oil phase is passed in the drying tower containing Calcium Chloride Powder Anhydrous and is dried, finally dried oil phase is passed into load cupric chloride is housed, in the 10X molecular sieve tower of Cerium II Chloride, carry out absorbing and deodorizing, finally obtain the POV turps product of sulfur-bearing 10-20ppm.This method operation is more loaded down with trivial details, and the use of clorox easily makes product produce chloride ion contamination.
U.S. Pat 2459570 and US3660512 have also adopted clorox as oxygenant, and in oxidation CST, after sulphur component, rectifying obtains refining turps product, equally also has the problems referred to above.
U.S. Pat 2409614, a kind of method of CST desulfuration purification is disclosed, first with air, CST is oxidized, afterwards its rectification under vacuum is collected to component, the more difficult control of not only atmospheric oxidation process of this method, and also selectivity is also lower, it is excessive easily terpenes to be oxidized, cause target product loss, when atmospheric oxidation simultaneously, also easily generate terpene superoxide, cause potential safety hazard.
In a word, not only there are various problems in above each method in technique, and be difficult to obtain super low sulfur firpene product.Therefore be necessary the method for the CST desulfuration purification that invention desulfuration efficiency is higher, environment is more friendly, production cost is lower, industrial reliability is stronger, to meet industrial needs.
Summary of the invention
The present invention has overcome the deficiency in existing method, proposes the terebinthine process for purification of a kind of crude sulphate; Its binding substances logos and chemical method, adopt the methods such as rectifying, oxidation, absorption and alkali cleaning to refine crude sulphate turps, is wherein oxidized and adsorbs and carry out simultaneously, and technique is simple, environmentally friendly, cost is lower.
Concrete technical scheme of the present invention is as follows:
The terebinthine process for purification of a kind of crude sulphate, comprises the steps:
(1) by the heat exchange of crude sulphate turps to 40-70 ℃, then enter in flashing tower and carry out flash separation, the boiling point flowing out from flashing tower tower top enters alkali lower than the trechmannite such as thioether, the mercaptan component of α-pinene and absorption system carries out directly discharging after neutralizing treatment; Collect the material that flashing tower tower bottom flow goes out, delivered to vacuum rectifying tower middle part and carry out rectifying separation;
(2) the low-sulfur terpene blend heat exchange of flowing out from vacuum rectifying tower tower top, to 60-110 ℃, then enters oxidation-adsorption tower and carries out oxidation-adsorption processing, when wherein residual sulfide is oxidized, also material is carried out to adsorption desulfurize processing; The boiling point going out from vacuum rectifying tower tower bottom flow is delivered to oil tank higher than the sulfurous organic compound of beta-pinene and other high boiling point terpenoid and carries out subsequent disposal;
(3) carry out oxidation-adsorption material after treatment and enter in alkali cleaning reactor, adopt alkaline solution to carry out alkali cleaning;
(4) enter in phase splitter through the material after alkali cleaning, the lower floor's alkalescence water after phase splitter layering flow in alkali and absorption system as the alkali source of this system; The upper oil phase obtaining after layering enters in the vacuum rectifying tower with lateral line discharging and separates, the a small amount of water flowing out from vacuum rectifying tower tower top with lateral line discharging and remaining trechmannite component stream are to alkali and absorption system, α-pinene product below vacuum rectifying tower top side line extraction sulphur content 5ppm with lateral line discharging, the beta-pinene product below the vacuum rectifying tower bottom side line extraction sulphur content 5ppm with lateral line discharging; The material of discharging at the bottom of the vacuum rectifying tower tower with lateral line discharging is delivered to oil tank and is carried out subsequent disposal.
In step (1), flashing tower divides two sections, and epimere is flash zone, and hypomere is filler segregation section, and the aspect ratio of two sections is 1:0.5-2; Flash zone flash vaporization point is 70-120 ℃, preferably 75-90 ℃; Filler segregation section tower bottom reboiler temperature is 90-130 ℃, preferably 100-110 ℃.Flash vaporization point and reboiler temperature are selected in to this scope and can effectively separate trechmannite component, reduced the loss of firpene product simultaneously.
For making vacuum rectifying tower reach best separating effect, minimum energy consumption, in step (1), vacuum rectifying tower tower top pressure is 4-20kPa, preferably 10-15Kpa; Tower top temperature is 55-105 ℃, preferably 80-95 ℃; Reflux ratio is 0.8-4, preferably 1-2.
In step (4), be 6-20kPa with the vacuum rectifying tower tower top pressure of lateral line discharging, tower top temperature is 40-65 ℃, and reflux ratio is 8-30.
In step (2), the temperature of oxidation-adsorption processing is 60-120 ℃, and the time is 0.1-2h, selects this treatment temp and treatment time sulphur component fully can be reacted and adsorbed.
Absorption carrier in described oxidation-adsorption tower is desulphurized aetivated carbon or the molecular sieve that load has oxygenant, and described oxygenant is sulfonation titanium cyanogen cobalt or poly-titanium cyanogen cobalt, and the quality of oxygenant accounts for 2 ‰ of absorption carrier total mass-20 ‰; Adopt above-mentioned absorption carrier can guarantee sulfocompound fully oxidized and absorption therein.
In step (3), alkaline solution is selected from the one in sodium carbonate solution, sodium hydroxide solution, solution of potassium carbonate, potassium hydroxide solution, and in alkaline solution, the quality percentage composition of solute is 3-20%; Select the alkaline solution of this concentration can be fully in and sulfuric acid component in material, simultaneously again little to equipment corrosion.
For sulfuric acid component in material is fully neutralized, the alkali cleaning time in step (3) is 0.1-2h.
In step (4), the service temperature of phase splitter is 40-70 ℃, and the residence time of material in phase splitter is 0.5h-2h.Select this service temperature and time can guarantee that profit two-phase thoroughly separates, avoided because entering the too low rectifying energy consumption that increases of temperature of charge with side line vacuum rectifying tower simultaneously.
Tool of the present invention has the following advantages:
1. the present invention adopts the flashing tower structure of top flash zone, bottom band filler segregation section, material mid-boiling point can be separated totally substantially lower than the trechmannite such as thioether, the mercaptan component of α-pinene.
2. the absorption carrier that the present invention adopts, compared to conventional oxidation catalyzer, desulfuration selectivity is high, effective, and amount of by-products is low, and product yield is high,
3. the present invention adopts the method that rectifying, absorption combine with chemical oxidation, can obtain super low sulfur firpene product.
4. the inventive method is simple, and lower, the industrial reliability of energy consumption and production cost is stronger.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the terebinthine process for purification of crude sulphate of the present invention.
Embodiment
The equipment that embodiment adopts is pilot plant, and wherein flashing tower T-1 internal diameter is 0.4m, point two sections, and epimere is flash zone, and hypomere is filler segregation section, and upper and lower section is highly respectively 2m and 3m, filler floor height 2m in filler segregation section; Vacuum rectifying tower T-2 height overall 14m, internal diameter 0.3m, its filler floor height 10m; Two tower A-1, A-2 of oxidation-adsorption tower, wherein a tower is stand-by still, volume is 0.5m
3, aspect ratio 10:1; Alkali cleaning reactor R-1 volume is 0.5m
3, aspect ratio is 2:1; Phase splitter S-1 volume is 0.5m
3, aspect ratio is 2:1; The vacuum rectifying tower T-3 of lateral line discharging, height overall 16m, internal diameter 0.3m, filler floor height 12m.
Material composition gas Chromatographic Determination in the present invention, sulphur content is measured by microcomputer sulphur chlorine analyzers.
The quality group of crude sulphate turps raw material becomes: firpene (α-pinene and beta-pinene) 82%, and total sulfur is 1023ppm, moisture 0.3%, solid impurity 0.21%, all the other are other terpene component.
(1) crude sulphate turps raw material with the speed of 12kg/h by 55 ℃ of interchanger E-1 preheatings after, enter in flashing tower T-1 and carry out flash separation processing by pipeline 1, in flashing tower, temperature is 102 ℃, filler segregation section tower reactor reboiler temperature is 104 ℃.The boiling point being flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite such as thioether, the mercaptan component of α-pinene through pipeline 2, adopts existing method to carry out directly discharging after neutralizing treatment; And the first desulfurization material going out from flashing tower tower bottom flow (its sulphur content is 35.4ppm) exports to vacuum rectifying tower T-2 through pipeline 3 and carry out rectifying separation, vacuum rectifying tower T-2 tower top pressure is 15.4kPa, and tower top temperature is 97.4 ℃, and reflux ratio is 1.3.
(2) boiling point going out from vacuum rectifying tower T-2 tower bottom flow is delivered to oil tank higher than the sulfurous organic compound of beta-pinene and other high boiling point terpenoid through pipeline 5 and carries out subsequent disposal.The low-sulfur terpene blend flowing out from vacuum rectifying tower T-2 tower top is through sampling analysis measuring, and its sulphur content is 21ppm.This low-sulfur terpene blend material, after interchanger E-2 heat exchange to 80 ℃, is sent in oxidation-adsorption tower A-1 and is carried out oxidation-adsorption processing by pipeline 6, and oxidation-adsorption treatment temp is 93 ℃, and the time is 2h.In oxidation-adsorption tower A-1, loaded the desulphurized aetivated carbon that load has sulfonation titanium cyanogen cobalt, the quality of desulphurized aetivated carbon is 200kg, and the quality of sulfonation titanium cyanogen cobalt catalyst is 4kg.
(3) entered in alkali cleaning reactor R-1 by pipeline 7 through oxidation-adsorption material after treatment, pass into aqueous sodium carbonate to alkali cleaning reactor R-1 with the speed of 5kg/h, in aqueous sodium carbonate, the quality percentage composition of sodium carbonate is 6%, fully stir, the residence time of material in alkali cleaning reactor R-1 is 0.5h.
(4) after alkali cleaning, material enters phase splitter S-1 through pipeline 8, and the service temperature of phase splitter S-1 is 65 ℃, and the residence time is 1.5h, separate profit two-phase, lower floor after phase splitter layering alkalescence water deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill at the vacuum rectifying tower T-3 middle part that the upper oil phase obtaining after layering enters lateral line discharging by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 10.2kPa, tower top temperature is that 48.4 ℃, reflux ratio are 20, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and micro-trechmannite component, they are delivered in alkali and carry out neutralizing treatment with absorption system R-2 through pipeline 12; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene products, is 2.5ppm through its sulphur content of sampling analysis measuring; The vacuum rectifying tower bottom side line of lateral line discharging, through pipeline 10 extraction super low sulfur beta-pinene products, is 4.2ppm through its sulphur content of sampling analysis measuring.At the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, through high boiling point terpenoid and the impurity of pipeline 11 extraction, send to oil tank by pipeline 16 and carry out subsequent disposal.
The quality group of crude sulphate turps raw material becomes: firpene (α-pinene and beta-pinene) 88%, and total sulfur is 897ppm, moisture 0.35%, solid impurity 0.33%, all the other are other terpene component.
(1) crude sulphate turps raw material is preheated to after 60 ℃ by interchanger E-1 with the speed of 14kg/h, is entered in flashing tower T-1 and is carried out flash separation processing by pipeline 1, and in flashing tower, temperature is 101 ℃, and filler segregation section tower reactor reboiler temperature is 103 ℃.The boiling point being flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite such as thioether, the mercaptan component of α-pinene through pipeline 2, adopts existing method to carry out directly discharging after neutralizing treatment; And the first desulfurization material going out from flashing tower tower bottom flow (its sulphur content is 32.3ppm) exports to and vacuum rectifying tower T-2, carries out rectifying separation through pipeline 3.Vacuum rectifying tower T-2 tower top pressure is 17.6kPa, and tower top temperature is 100.6 ℃, and reflux ratio is 1.6.
(2) boiling point going out from vacuum rectifying tower T-2 tower bottom flow is delivered to oil tank higher than the sulfurous organic compound of beta-pinene and other high boiling point terpenoid through pipeline 5 and carries out subsequent disposal.The low-sulfur terpene blend flowing out from vacuum rectifying tower T-2 tower top is through sampling analysis measuring, and its sulphur content is 18ppm.This low-sulfur terpene blend material, after interchanger E-2 heat exchange to 98 ℃, is sent in oxidation-adsorption tower A-1 and is carried out oxidation-adsorption processing by pipeline 6, and oxidation-adsorption treatment temp is 100 ℃, and the time is 1.5h.In oxidation-adsorption tower A-1, loaded the desulphurized aetivated carbon that load has sulfonation titanium cyanogen cobalt, the quality of desulphurized aetivated carbon is 200kg, and the quality of sulfonation titanium cyanogen cobalt catalyst is 2 kg.
(3) entered in alkali cleaning reactor R-1 by pipeline 7 through oxidation-adsorption material after treatment, pass into aqueous sodium carbonate to alkali cleaning reactor R-1 with the speed of 4.6kg/h, in aqueous sodium carbonate, the quality percentage composition of sodium carbonate is 5.6%, fully stir, the residence time of material in alkali cleaning reactor R-1 is 0.5h.
(4) after alkali cleaning, material enters phase splitter S-1 through pipeline 8, and the service temperature of phase splitter S-1 is 55 ℃, and the residence time is 1.8h, separate profit two-phase, lower floor after phase splitter layering alkalescence water deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill at the vacuum rectifying tower T-3 middle part that the upper oil phase obtaining after layering enters lateral line discharging by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 15.1kPa, tower top temperature is that 55.2 ℃, reflux ratio are 16, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and micro-trechmannite component, they are delivered in alkali and carry out neutralizing treatment with absorption system R-2 through pipeline 12; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene products, is 3.1ppm through its sulphur content of sampling analysis measuring; The vacuum rectifying tower bottom side line of lateral line discharging is through pipeline 10 extraction super low sulfur beta-pinene products, through its sulphur content of sampling analysis measuring 3.6ppm.At the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, through high boiling point terpenoid and the impurity of pipeline 11 extraction, send to oil tank by pipeline 16 and carry out subsequent disposal.
The quality group of crude sulphate turps raw material becomes: firpene (α-pinene and beta-pinene) 81%, and total sulfur is 623ppm, moisture 0.31%, solid impurity 0.19%, all the other are other terpene component.
(1) crude sulphate turps raw material is preheated to after 66 ℃ by interchanger E-1 with the speed of 10kg/h, is entered in flashing tower T-1 and is carried out flash separation processing by pipeline 1, and in flashing tower, temperature is 105 ℃, and filler segregation section tower reactor reboiler temperature is 107 ℃.The boiling point being flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite such as thioether, the mercaptan component of α-pinene through pipeline 2, adopts existing method to carry out directly discharging after neutralizing treatment; And the first desulfurization material going out from flashing tower tower bottom flow (its sulphur content is 33.7ppm) exports to vacuum rectifying tower T-2 through pipeline 3 and carry out rectifying separation, vacuum rectifying tower T-2 tower top pressure is 8.8kPa, and tower top temperature is 78.2 ℃, and reflux ratio is 1.8.
(2) boiling point going out from vacuum rectifying tower T-2 tower bottom flow is delivered to oil tank higher than the sulfurous organic compound of beta-pinene and other high boiling point terpenoid through pipeline 5 and carries out subsequent disposal.The low-sulfur terpene blend flowing out from vacuum rectifying tower T-2 tower top is through sampling analysis measuring, and its sulphur content is 19ppm.This low-sulfur terpene blend material, after interchanger E-2 heat exchange to 70 ℃, is sent in oxidation-adsorption tower A-1 and is carried out oxidation-adsorption processing by pipeline 6, and oxidation-adsorption treatment temp is 83 ℃, and the time is 2h.In oxidation-adsorption tower A-1, loaded the desulphurized aetivated carbon that load has poly-titanium cyanogen cobalt, the quality of desulphurized aetivated carbon is 200kg, and the quality of poly-titanium cyanogen cobalt catalyst is 1kg.
(3) entered in alkali cleaning reactor R-1 by pipeline 7 through oxidation-adsorption material after treatment, pass into wet chemical to alkali cleaning reactor R-1 with the speed of 6.8kg/h, in wet chemical, the quality percentage composition of sodium carbonate is 4.2%, fully stir, the residence time of material in alkali cleaning reactor R-1 is 0.6h.
(4) after alkali cleaning, material enters phase splitter S-1 through pipeline 8, and the service temperature of phase splitter S-1 is 45 ℃, and the residence time is 2h, separate profit two-phase, lower floor after phase splitter layering alkalescence water deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill at the vacuum rectifying tower T-3 middle part that the upper oil phase obtaining after layering enters lateral line discharging by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 17.8kPa, tower top temperature is that 58.8 ℃, reflux ratio are 16, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and micro-trechmannite component, they are delivered in alkali and carry out neutralizing treatment with absorption system R-2 through pipeline 12; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene products, is 2.9ppm through its sulphur content of sampling analysis measuring; The vacuum rectifying tower bottom side line of lateral line discharging, through pipeline 10 extraction super low sulfur beta-pinene products, is 4.1ppm through its sulphur content of sampling analysis measuring.At the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, through high boiling point terpenoid and the impurity of pipeline 11 extraction, send to oil tank by pipeline 16 and carry out subsequent disposal.
embodiment 4
The quality group of crude sulphate turps raw material becomes: firpene (α-pinene and beta-pinene) 90.1%, and total sulfur is 763ppm, moisture 0.42%, solid impurity 0.26%, all the other are other terpene component.
(1) crude sulphate turps raw material is preheated to after 70 ℃ by interchanger E-1 with the speed of 11kg/h, is entered in flashing tower T-1 and is carried out flash separation processing by pipeline 1, and in flashing tower, temperature is 104 ℃, and filler segregation section tower reactor reboiler temperature is 106 ℃.The boiling point being flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite such as thioether, the mercaptan component of α-pinene through pipeline 2, adopts existing method to carry out directly discharging after neutralizing treatment; And the first desulfurization material going out from flashing tower tower bottom flow (its sulphur content is 32ppm) exports to vacuum rectifying tower T-2 through pipeline 3 and carry out rectifying separation, vacuum rectifying tower T-2 tower top pressure is 9.6kPa, and tower top temperature is 84 ℃, and reflux ratio is 1.5.
(2) boiling point going out from vacuum rectifying tower T-2 tower bottom flow is delivered to oil tank higher than the sulfurous organic compound of beta-pinene and other high boiling point terpenoid through pipeline 5 and carries out subsequent disposal.The low-sulfur terpene blend flowing out from vacuum rectifying tower T-2 tower top is through sampling analysis measuring, and its sulphur content is 23ppm.This low-sulfur terpene blend material, after interchanger E-2 heat exchange to 102 ℃, is sent in oxidation-adsorption tower A-1 and is carried out oxidation-adsorption processing by pipeline 6, and oxidation-adsorption treatment temp is 115 ℃, and the time is 0.5h.In oxidation-adsorption tower A-1, loaded the molecular sieve that load has sulfonation titanium cyanogen cobalt, the quality of molecular sieve is 200kg, and the quality of sulfonation titanium cyanogen cobalt catalyst is 1.5kg.
(3) entered in alkali cleaning reactor R-1 by pipeline 7 through oxidation-adsorption material after treatment, pass into aqueous sodium hydroxide solution to alkali cleaning reactor R-1 with the speed of 7.1kg/h, in aqueous sodium hydroxide solution, the quality percentage composition of sodium carbonate is 4.4%, fully stir, the residence time of material in alkali cleaning reactor R-1 is 0.4h.
(4) after alkali cleaning, material enters phase splitter S-1 through pipeline 8, and the service temperature of phase splitter S-1 is 48 ℃, and the residence time is 1h, separate profit two-phase, lower floor after phase splitter layering alkalescence water deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill at the vacuum rectifying tower T-3 middle part that the upper oil phase obtaining after layering enters lateral line discharging by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 13.6kPa, tower top temperature is that 54 ℃, reflux ratio are 16, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and micro-trechmannite component, they are delivered in alkali and carry out neutralizing treatment with absorption system R-2 through pipeline 12; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene products, is 2.3ppm through its sulphur content of sampling analysis measuring; The vacuum rectifying tower bottom side line of lateral line discharging, through pipeline 10 extraction super low sulfur beta-pinene products, is 3.8ppm through its sulphur content of sampling analysis measuring.At the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, through high boiling point terpenoid and the impurity of pipeline 11 extraction, send to oil tank by pipeline 16 and carry out subsequent disposal.
Oxidation-adsorption tower A-1 in the middle of embodiment, wherein load has the desulphurized aetivated carbon of oxygenant or molecular sieve use regenerate or change for about two months to half a year.
Claims (9)
1. the terebinthine process for purification of crude sulphate, is characterized in that comprising the steps:
(1) by the heat exchange of crude sulphate turps to 40-70 ℃, then enter in flashing tower and carry out flash separation, the boiling point flowing out from flashing tower tower top enters alkali lower than the trechmannite such as thioether, the mercaptan component of α-pinene and absorption system carries out directly discharging after neutralizing treatment; Collect the material that flashing tower tower bottom flow goes out, delivered to vacuum rectifying tower middle part and carry out rectifying separation;
(2) the low-sulfur terpene blend heat exchange of flowing out from vacuum rectifying tower tower top, to 60-110 ℃, then enters oxidation-adsorption tower and carries out oxidation-adsorption processing, when wherein residual sulfide is oxidized, also material is carried out to adsorption desulfurize processing; The boiling point going out from vacuum rectifying tower tower bottom flow is delivered to oil tank higher than the sulfurous organic compound of beta-pinene and other high boiling point terpenoid and carries out subsequent disposal;
(3) carry out oxidation-adsorption material after treatment and enter in alkali cleaning reactor, adopt alkaline solution to carry out alkali cleaning;
(4) enter in phase splitter through the material after alkali cleaning, the lower floor's alkalescence water after phase splitter layering flow in alkali and absorption system as the alkali source of this system; The upper oil phase obtaining after layering enters in the vacuum rectifying tower with lateral line discharging and separates, the a small amount of water flowing out from vacuum rectifying tower tower top with lateral line discharging and remaining trechmannite component stream are to alkali and absorption system, α-pinene product below vacuum rectifying tower top side line extraction sulphur content 5ppm with lateral line discharging, the beta-pinene product below the vacuum rectifying tower bottom side line extraction sulphur content 5ppm with lateral line discharging; The material of discharging at the bottom of the vacuum rectifying tower tower with lateral line discharging is delivered to oil tank and is carried out subsequent disposal.
2. the terebinthine process for purification of crude sulphate according to claim 1, is characterized in that in step (1), flashing tower divides two sections, and epimere is flash zone, and hypomere is filler segregation section, and the aspect ratio of two sections is 1:0.5-2; Flash zone flash vaporization point is 70-120 ℃, and filler segregation section tower bottom reboiler temperature is 90-130 ℃.
3. the terebinthine process for purification of crude sulphate according to claim 1, is characterized in that in step (1), vacuum rectifying tower tower top pressure is 4-20kPa, and tower top temperature is 55-105 ℃, and reflux ratio is 0.8-4.
4. the terebinthine process for purification of crude sulphate according to claim 1, is characterized in that in step (4), the vacuum rectifying tower tower top pressure with lateral line discharging is 6-20kPa, and tower top temperature is 40-65 ℃, and reflux ratio is 8-30.
5. the terebinthine process for purification of crude sulphate according to claim 1, is characterized in that the temperature of oxidation-adsorption processing in step (2) is 60-120 ℃, and the time is 0.1-2h.
6. the terebinthine process for purification of crude sulphate according to claim 5, it is characterized in that the absorption carrier in described oxidation-adsorption tower is desulphurized aetivated carbon or the molecular sieve that load has oxygenant, described oxygenant is sulfonation titanium cyanogen cobalt or poly-titanium cyanogen cobalt, and the quality of oxygenant accounts for 2 ‰ of absorption carrier total mass-20 ‰.
7. the terebinthine process for purification of crude sulphate according to claim 1, it is characterized in that in step (3), alkaline solution is selected from the one in sodium carbonate solution, sodium hydroxide solution, solution of potassium carbonate, potassium hydroxide solution, in alkaline solution, the quality percentage composition of solute is 3-20%.
8. the terebinthine process for purification of crude sulphate according to claim 7, is characterized in that the alkali cleaning time in step (3) is 0.1-2h.
9. the terebinthine process for purification of crude sulphate according to claim 1, is characterized in that the service temperature of phase splitter in step (4) is 40-70 ℃, and the residence time of material in phase splitter is 0.5h-2h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410080213.XA CN103787818B (en) | 2014-03-06 | 2014-03-06 | A kind of process for purification of crude sulfate turpentine |
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| CN201410080213.XA CN103787818B (en) | 2014-03-06 | 2014-03-06 | A kind of process for purification of crude sulfate turpentine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106281041A (en) * | 2016-08-22 | 2017-01-04 | 怀化市双阳林化有限公司 | The deodorization of a kind of crude sulfate turpentine and the production method of sulfate turpentine |
| CN109762470A (en) * | 2019-01-23 | 2019-05-17 | 厦门中坤化学有限公司 | A kind of sulfate turpentine desulfurization refining method of ultra-low sulfur |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2409614A (en) * | 1942-01-15 | 1946-10-22 | Hercules Powder Co Ltd | Refining sulfate turpentine |
| CN102796457A (en) * | 2011-10-26 | 2012-11-28 | 江西理工大学 | New method for refining coarse sulfate turpentine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2409614A (en) * | 1942-01-15 | 1946-10-22 | Hercules Powder Co Ltd | Refining sulfate turpentine |
| CN102796457A (en) * | 2011-10-26 | 2012-11-28 | 江西理工大学 | New method for refining coarse sulfate turpentine |
Non-Patent Citations (1)
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| 陈磊等: "粗硫酸盐松节油精制研究", 《食品和机械》, vol. 29, no. 1, 18 January 2013 (2013-01-18), pages 223 - 225 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106281041A (en) * | 2016-08-22 | 2017-01-04 | 怀化市双阳林化有限公司 | The deodorization of a kind of crude sulfate turpentine and the production method of sulfate turpentine |
| CN106281041B (en) * | 2016-08-22 | 2019-01-04 | 湖南双阳高科化工有限公司 | A kind of deodorization of crude sulfate turpentine and the production method of sulfate turpentine |
| CN109762470A (en) * | 2019-01-23 | 2019-05-17 | 厦门中坤化学有限公司 | A kind of sulfate turpentine desulfurization refining method of ultra-low sulfur |
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| CN103787818B (en) | 2015-09-02 |
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