CN103787818B - A kind of process for purification of crude sulfate turpentine - Google Patents
A kind of process for purification of crude sulfate turpentine Download PDFInfo
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Abstract
The present invention relates to a kind of process for purification of crude sulfate turpentine, comprising the steps: that (1) carries out flash separation by entering in flashing tower after CST heat exchange, collect the material that flashing tower tower bottom flow goes out, delivered in the middle part of vacuum rectifying tower and carry out rectifying separation; (2) after the material-heat-exchanging of vacuum rectifying tower tower top outflow, enter oxidation-adsorption tower and carry out oxidation-adsorption process; (3) material after oxidation-adsorption process enters in alkali cleaning reactor, adopts alkaline solution to carry out alkali cleaning; (4) material after alkali cleaning enters in phase splitter, and the upper oil phase obtained after layering enters in the vacuum rectifying tower of band lateral line discharging and is separated, from top side take-off α-pinene product, and bottom side take-off beta-pinene product.The present invention adopts rectifying, adsorbs the method combined with chemical oxidation, can obtain super low sulfur firpene product.The inventive method is simple, energy consumption and lower, the industrial reliability of production cost stronger.
Description
Invention field
The present invention relates to turps, the desulfurization being specifically related to crude sulfate turpentine is purified, and relates to a kind of super low sulfur firpene product purification method of crude sulfate turpentine more specifically.
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 gum turpentine, crude sulfate turpentine (hereinafter referred to as CST), steam-distilled(wood)turpentine, destructive distillation turpentine four kinds.China is main based on gum turpentine.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 that raw material produces the by product of paper pulp by sulphate process with pine, 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 Downstream Products be directly used in, need through desulfuration purification, make it reach certain specification, use through the alternative gum turpentine of refining CST, as as products such as Material synthesis Terpineol 350, 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%.CST's is refining mainly to its desulfurization, and process for purification relatively more conventional at present has Physical, chemical method and treatment process that the two is combined; Usually chemical method is combined with Physical to reach good refining effect.
(food and machinery, 2013,29 such as Chen Lei, 1) a kind of CST desulfurization refining method is disclosed, first carry out wet distillation after being utilized by CST NaOH to wash, afterwards with a certain amount of zinc oxide process, finally utilize charcoal absorption to obtain the turps after refining.
Chinese patent CN101654595A, disclose a kind of method of CST desulfuration purification, a certain amount of oxygenant terpene hydroperoxide and CST are reacted, wash layering with water afterwards, take out oil phase, oil phase rectifying collected the distillate of different boiling, obtains sulphur content lower than 20ppm and almost do not 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, disclose a kind of CST process for purification, first special rectification under vacuum method is adopted to collect the cut of different boiling, recycle certain density chlorine bleach liquor to be oxidized cut, product after oxidation adds a certain proportion of water again and carries out washing 2-3 rear stratification, removing aqueous phase, oil phase is passed in the drying tower containing Calcium Chloride Powder Anhydrous and carry out drying, finally dried oil phase is passed into and load cupric chloride is housed, absorbing and deodorizing is carried out in the 10X molecular sieve tower of Cerium II Chloride, finally obtain the POV turps product of sulfur-bearing 10-20ppm.The operation of this method is more loaded down with trivial details, and the use of clorox easily makes product produce chloride ion contamination.
US Patent No. 2459570 and US3660512 also have employed clorox as oxygenant, and in oxidation CST, after sulphur component, rectifying obtains the turps product refined, and equally also there are the problems referred to above.
US Patent No. 2409614, disclose a kind of method of CST desulfuration purification, first with air, CST is oxidized, afterwards component is collected in its rectification under vacuum, the more difficult control of this method not only atmospheric oxidation process, and selectivity is also lower, it is excessive to be easily oxidized by terpenes, cause target product to lose, also easily generate terpene superoxide during atmospheric oxidation simultaneously, cause potential safety hazard.
In a word, not only there is various problem in above each method in technique, and be difficult to obtain super low sulfur firpene product.Therefore 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 is necessary, to meet industrial needs.
Summary of the invention
Instant invention overcomes the deficiency in existing method, propose a kind of process for purification of crude sulfate turpentine; Its binding substances logos and chemical method, adopt the method such as rectifying, oxidation, absorption and alkali cleaning to refine crude sulfate turpentine, be wherein oxidized and adsorb and carry out simultaneously, technique is simple, environmentally friendly, cost is lower.
Concrete technical scheme of the present invention is as follows:
A process for purification for crude sulfate turpentine, comprises the steps:
(1) by crude sulfate turpentine heat exchange to 40-70 DEG C, then enter in flashing tower and carry out flash separation, the boiling point flowed out from flashing tower tower top enter alkali lower than the trechmannite component such as thioether, mercaptan of α-pinene and absorption system carry out neutralizing treatment after directly discharge; Collect the material that flashing tower tower bottom flow goes out, delivered in the middle part of vacuum rectifying tower 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 DEG C, then enters oxidation-adsorption tower and carries out oxidation-adsorption process, while being oxidized, also carry out adsorption desulfurize process to material to wherein residual sulfide; The boiling point gone 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) material after carrying out oxidation-adsorption process enters in alkali cleaning reactor, adopts alkaline solution to carry out alkali cleaning;
(4) material after alkali cleaning enters in phase splitter, lower floor after phase splitter layering alkalescence aqueous phase flow in alkali and absorption system as the alkali source of this system; The upper oil phase obtained after layering enters in the vacuum rectifying tower of band lateral line discharging and is separated, the a small amount of water flowed out from the vacuum rectifying tower tower top of band lateral line discharging and remaining trechmannite component flow to alkali and absorption system, the α-pinene product of vacuum rectifying tower top below the side take-off sulphur content 5ppm with lateral line discharging, the beta-pinene product of vacuum rectifying tower bottom below the side take-off sulphur content 5ppm of band lateral line discharging; Material with discharging at the bottom of the vacuum rectifying tower tower of 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 DEG C, preferred 75-90 DEG C; Filler segregation section tower bottom reboiler temperature is 90-130 DEG C, preferred 100-110 DEG C.Flash vaporization point and reboiler temperature are selected in this scope and can be effectively separated trechmannite component, reduce the loss of firpene product simultaneously.
For the separating effect making vacuum rectifying tower reach best, minimum energy consumption, in step (1), vacuum rectifying tower tower top pressure is 4-20kPa, preferred 10-15Kpa; Tower top temperature is 55-105 DEG C, preferred 80-95 DEG C; Reflux ratio is 0.8-4, preferred 1-2.
In step (4), the vacuum rectifying tower tower top pressure of band lateral line discharging is 6-20kPa, and tower top temperature is 40-65 DEG C, and reflux ratio is 8-30.
In step (2), the temperature of oxidation-adsorption process is 60-120 DEG C, 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 ‰-20 ‰ of absorption carrier total mass; Adopt above-mentioned absorption carrier can ensure sulfocompound fully oxidized and absorption wherein.
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 mass percentage of solute is 3-20%; Select this concentration alkaline solution can fully in and material in sulfuric acid component, simultaneously little again to equipment corrosion.
For making sulfuric acid component in material fully neutralize, the alkali cleaning time in step (3) is 0.1-2h.
In step (4), the service temperature of phase splitter is 40-70 DEG C, and the residence time of material in phase splitter is 0.5h-2h.Selecting this service temperature and time can ensure that water-oil phase thoroughly separates, avoiding temperature of charge because entering band side line vacuum rectifying tower too low and increase energy consumption of rectification simultaneously.
Tool of the present invention has the following advantages:
1. the present invention adopts the flashing tower structure of top flash zone, lower bands filler segregation section, the trechmannite component such as thioether, mercaptan of material mid-boiling point lower than α-pinene can be separated totally substantially.
2. the absorption carrier of the present invention's employing, 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 rectifying, adsorbs the method combined with chemical oxidation, can obtain super low sulfur firpene product.
4. the inventive method is simple, energy consumption and lower, the industrial reliability of production cost stronger.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the process for purification of crude sulfate turpentine 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 towers A-1, A-2 of oxidation-adsorption tower, wherein a tower is stand-by still, and 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.
embodiment 1
The quality group of crude sulfate turpentine raw material becomes: firpene (α-pinene and beta-pinene) 82%, and total sulfur is 1023ppm, moisture 0.3%, solid impurity 0.21%, and all the other are other terpene component.
(1) crude sulfate turpentine raw material is with the speed of 12kg/h by after interchanger E-1 preheating 55 DEG C, and entered in flashing tower T-1 by pipeline 1 and carry out flash separation process, in flashing tower, temperature is 102 DEG C, and filler segregation section tower reactor reboiler temperature is 104 DEG C.The boiling point flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite component such as thioether, mercaptan of α-pinene through pipeline 2, directly discharges after adopting existing method to carry out neutralizing treatment; And the first desulfurization material (its sulphur content is 35.4ppm) gone out from flashing tower tower bottom flow exports to vacuum rectifying tower T-2 through pipeline 3 and carries out rectifying separation, vacuum rectifying tower T-2 tower top pressure is 15.4kPa, and tower top temperature is 97.4 DEG C, and reflux ratio is 1.3.
(2) boiling point gone 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.From vacuum rectifying tower T-2 tower top flow out low-sulfur terpene blend through sampling analysis measuring, its sulphur content is 21ppm.This low-sulfur terpene blend material is after interchanger E-2 heat exchange to 80 DEG C, and sent in oxidation-adsorption tower A-1 by pipeline 6 and carry out oxidation-adsorption process, oxidation-adsorption treatment temp is 93 DEG C, and the time is 2h.Be loaded with the desulphurized aetivated carbon that load has sulfonation titanium cyanogen cobalt in oxidation-adsorption tower A-1, the quality of desulphurized aetivated carbon is 200kg, and the quality of sulfonation titanium cyanogen cobalt catalyst is 4kg.
(3) material after oxidation-adsorption process enters in alkali cleaning reactor R-1 by pipeline 7, aqueous sodium carbonate is passed into in alkali cleaning reactor R-1 with the speed of 5kg/h, in aqueous sodium carbonate, the mass percentage of sodium carbonate is 6%, abundant stirring, 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 DEG C, and the residence time is 1.5h, separate water-oil phase, lower floor after phase splitter layering alkalescence aqueous phase deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill in the middle part of the upper oil phase obtained after layering is then entered lateral line discharging vacuum rectifying tower T-3 by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 10.2kPa, tower top temperature is 48.4 DEG C, reflux ratio is 20, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and the trechmannite component of trace, they deliver in alkali through pipeline 12 and absorption system R-2 carries out neutralizing treatment; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene product, 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 product, is 4.2ppm through its sulphur content of sampling analysis measuring.Through the high boiling point terpenoid of pipeline 11 extraction and impurity at the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, then send to oil tank by pipeline 16 and carry out subsequent disposal.
embodiment 2
The quality group of crude sulfate turpentine raw material becomes: firpene (α-pinene and beta-pinene) 88%, and total sulfur is 897ppm, moisture 0.35%, solid impurity 0.33%, and all the other are other terpene component.
(1) after crude sulfate turpentine raw material is preheated to 60 DEG C with the speed of 14kg/h by interchanger E-1, is entered in flashing tower T-1 carry out flash separation process by pipeline 1, in flashing tower, temperature is 101 DEG C, and filler segregation section tower reactor reboiler temperature is 103 DEG C.The boiling point flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite component such as thioether, mercaptan of α-pinene through pipeline 2, directly discharges after adopting existing method to carry out neutralizing treatment; And export to vacuum rectifying tower T-2 through pipeline 3 carry out rectifying separation from the first desulfurization material (its sulphur content is 32.3ppm) that flashing tower tower bottom flow goes out.Vacuum rectifying tower T-2 tower top pressure is 17.6kPa, and tower top temperature is 100.6 DEG C, and reflux ratio is 1.6.
(2) boiling point gone 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.From vacuum rectifying tower T-2 tower top flow out low-sulfur terpene blend through sampling analysis measuring, its sulphur content is 18ppm.This low-sulfur terpene blend material is after interchanger E-2 heat exchange to 98 DEG C, and sent in oxidation-adsorption tower A-1 by pipeline 6 and carry out oxidation-adsorption process, oxidation-adsorption treatment temp is 100 DEG C, and the time is 1.5h.Be loaded with the desulphurized aetivated carbon that load has sulfonation titanium cyanogen cobalt in oxidation-adsorption tower A-1, the quality of desulphurized aetivated carbon is 200kg, and the quality of sulfonation titanium cyanogen cobalt catalyst is 2 kg.
(3) material after oxidation-adsorption process enters in alkali cleaning reactor R-1 by pipeline 7, aqueous sodium carbonate is passed into in alkali cleaning reactor R-1 with the speed of 4.6kg/h, in aqueous sodium carbonate, the mass percentage of sodium carbonate is 5.6%, abundant stirring, 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 DEG C, and the residence time is 1.8h, separate water-oil phase, lower floor after phase splitter layering alkalescence aqueous phase deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill in the middle part of the upper oil phase obtained after layering is then entered lateral line discharging vacuum rectifying tower T-3 by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 15.1kPa, tower top temperature is 55.2 DEG C, reflux ratio is 16, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and the trechmannite component of trace, they deliver in alkali through pipeline 12 and absorption system R-2 carries out neutralizing treatment; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene product, is 3.1ppm 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 product, through its sulphur content 3.6ppm of sampling analysis measuring.Through the high boiling point terpenoid of pipeline 11 extraction and impurity at the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, then send to oil tank by pipeline 16 and carry out subsequent disposal.
embodiment 3
The quality group of crude sulfate turpentine raw material becomes: firpene (α-pinene and beta-pinene) 81%, and total sulfur is 623ppm, moisture 0.31%, solid impurity 0.19%, and all the other are other terpene component.
(1) after crude sulfate turpentine raw material is preheated to 66 DEG C with the speed of 10kg/h by interchanger E-1, is entered in flashing tower T-1 carry out flash separation process by pipeline 1, in flashing tower, temperature is 105 DEG C, and filler segregation section tower reactor reboiler temperature is 107 DEG C.The boiling point flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite component such as thioether, mercaptan of α-pinene through pipeline 2, directly discharges after adopting existing method to carry out neutralizing treatment; And the first desulfurization material (its sulphur content is 33.7ppm) gone out from flashing tower tower bottom flow exports to vacuum rectifying tower T-2 through pipeline 3 and carries out rectifying separation, vacuum rectifying tower T-2 tower top pressure is 8.8kPa, and tower top temperature is 78.2 DEG C, and reflux ratio is 1.8.
(2) boiling point gone 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.From vacuum rectifying tower T-2 tower top flow out low-sulfur terpene blend through sampling analysis measuring, its sulphur content is 19ppm.This low-sulfur terpene blend material is after interchanger E-2 heat exchange to 70 DEG C, and sent in oxidation-adsorption tower A-1 by pipeline 6 and carry out oxidation-adsorption process, oxidation-adsorption treatment temp is 83 DEG C, and the time is 2h.Be loaded with the desulphurized aetivated carbon that load has poly-titanium cyanogen cobalt in oxidation-adsorption tower A-1, the quality of desulphurized aetivated carbon is 200kg, and the quality of poly-titanium cyanogen cobalt catalyst is 1kg.
(3) material after oxidation-adsorption process enters in alkali cleaning reactor R-1 by pipeline 7, wet chemical is passed into in alkali cleaning reactor R-1 with the speed of 6.8kg/h, in wet chemical, the mass percentage of sodium carbonate is 4.2%, abundant stirring, 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 DEG C, and the residence time is 2h, separate water-oil phase, lower floor after phase splitter layering alkalescence aqueous phase deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill in the middle part of the upper oil phase obtained after layering is then entered lateral line discharging vacuum rectifying tower T-3 by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 17.8kPa, tower top temperature is 58.8 DEG C, reflux ratio is 16, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and the trechmannite component of trace, they deliver in alkali through pipeline 12 and absorption system R-2 carries out neutralizing treatment; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene product, 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 product, is 4.1ppm through its sulphur content of sampling analysis measuring.Through the high boiling point terpenoid of pipeline 11 extraction and impurity at the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, then send to oil tank by pipeline 16 and carry out subsequent disposal.
embodiment 4
The quality group of crude sulfate turpentine raw material becomes: firpene (α-pinene and beta-pinene) 90.1%, and total sulfur is 763ppm, moisture 0.42%, solid impurity 0.26%, and all the other are other terpene component.
(1) after crude sulfate turpentine raw material is preheated to 70 DEG C with the speed of 11kg/h by interchanger E-1, is entered in flashing tower T-1 carry out flash separation process by pipeline 1, in flashing tower, temperature is 104 DEG C, and filler segregation section tower reactor reboiler temperature is 106 DEG C.The boiling point flowed out by flashing tower tower top exports in alkali and absorption system R-2 lower than the trechmannite component such as thioether, mercaptan of α-pinene through pipeline 2, directly discharges after adopting existing method to carry out neutralizing treatment; And the first desulfurization material (its sulphur content is 32ppm) gone out from flashing tower tower bottom flow exports to vacuum rectifying tower T-2 through pipeline 3 and carries out rectifying separation, vacuum rectifying tower T-2 tower top pressure is 9.6kPa, and tower top temperature is 84 DEG C, and reflux ratio is 1.5.
(2) boiling point gone 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.From vacuum rectifying tower T-2 tower top flow out low-sulfur terpene blend through sampling analysis measuring, its sulphur content is 23ppm.This low-sulfur terpene blend material is after interchanger E-2 heat exchange to 102 DEG C, and sent in oxidation-adsorption tower A-1 by pipeline 6 and carry out oxidation-adsorption process, oxidation-adsorption treatment temp is 115 DEG C, and the time is 0.5h.Be loaded with the molecular sieve that load has sulfonation titanium cyanogen cobalt in oxidation-adsorption tower A-1, the quality of molecular sieve is 200kg, and the quality of sulfonation titanium cyanogen cobalt catalyst is 1.5kg.
(3) material after oxidation-adsorption process enters in alkali cleaning reactor R-1 by pipeline 7, aqueous sodium hydroxide solution is passed into in alkali cleaning reactor R-1 with the speed of 7.1kg/h, in aqueous sodium hydroxide solution, the mass percentage of sodium carbonate is 4.4%, abundant stirring, 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 DEG C, and the residence time is 1h, separate water-oil phase, lower floor after phase splitter layering alkalescence aqueous phase deliver in alkali via pipeline 14 and absorption system R-2 as the alkali source of this system; Distill in the middle part of the upper oil phase obtained after layering is then entered lateral line discharging vacuum rectifying tower T-3 by pipeline 9.The vacuum rectifying tower T-3 tower top pressure of lateral line discharging is 13.6kPa, tower top temperature is 54 DEG C, reflux ratio is 16, from a small amount of water of vacuum rectifying tower overhead extraction of lateral line discharging and the trechmannite component of trace, they deliver in alkali through pipeline 12 and absorption system R-2 carries out neutralizing treatment; The vacuum rectifying tower top side line of lateral line discharging, through pipeline 13 extraction super low sulfur α-pinene product, 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 product, is 3.8ppm through its sulphur content of sampling analysis measuring.Through the high boiling point terpenoid of pipeline 11 extraction and impurity at the bottom of the vacuum rectifying tower T-3 tower of lateral line discharging, then 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 to use within about two months to half a year, to carry out regenerating or changing.
Claims (9)
1. a process for purification for crude sulfate turpentine, is characterized in that comprising the steps:
(1) by crude sulfate turpentine heat exchange to 40-70 DEG C, then enter in flashing tower and carry out flash separation, the boiling point flowed out from flashing tower tower top enter alkali lower than the trechmannite component such as thioether, mercaptan of α-pinene and absorption system carry out neutralizing treatment after directly discharge; Collect the material that flashing tower tower bottom flow goes out, delivered in the middle part of vacuum rectifying tower 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 DEG C, then enters oxidation-adsorption tower and carries out oxidation-adsorption process, while being oxidized, also carry out adsorption desulfurize process to material to wherein residual sulfide; The boiling point gone 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) material after carrying out oxidation-adsorption process enters in alkali cleaning reactor, adopts alkaline solution to carry out alkali cleaning;
(4) material after alkali cleaning enters in phase splitter, lower floor after phase splitter layering alkalescence aqueous phase flow in alkali and absorption system as the alkali source of this system; The upper oil phase obtained after layering enters in the vacuum rectifying tower of band lateral line discharging and is separated, the a small amount of water flowed out from the vacuum rectifying tower tower top of band lateral line discharging and remaining trechmannite component flow to alkali and absorption system, the α-pinene product of vacuum rectifying tower top below the side take-off sulphur content 5ppm with lateral line discharging, the beta-pinene product of vacuum rectifying tower bottom below the side take-off sulphur content 5ppm of band lateral line discharging; Material with discharging at the bottom of the vacuum rectifying tower tower of lateral line discharging is delivered to oil tank and is carried out subsequent disposal.
2. the process for purification of crude sulfate turpentine according to claim 1, it is characterized in that in step (1), flashing tower divides two sections, 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 DEG C, and filler segregation section tower bottom reboiler temperature is 90-130 DEG C.
3. the process for purification of crude sulfate turpentine according to claim 1, it is characterized in that in step (1), vacuum rectifying tower tower top pressure is 4-20kPa, tower top temperature is 55-105 DEG C, and reflux ratio is 0.8-4.
4. the process for purification of crude sulfate turpentine according to claim 1, it is characterized in that the vacuum rectifying tower tower top pressure of band lateral line discharging in step (4) is 6-20kPa, tower top temperature is 40-65 DEG C, and reflux ratio is 8-30.
5. the process for purification of crude sulfate turpentine according to claim 1, it is characterized in that the temperature of oxidation-adsorption process in step (2) is 60-120 DEG C, the time is 0.1-2h.
6. the process for purification of crude sulfate turpentine 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 ‰-20 ‰ of absorption carrier total mass.
7. the process for purification of crude sulfate turpentine 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 mass percentage of solute is 3-20%.
8. the process for purification of crude sulfate turpentine according to claim 7, is characterized in that the alkali cleaning time in step (3) is 0.1-2h.
9. the process for purification of crude sulfate turpentine according to claim 1, it is characterized in that the service temperature of phase splitter in step (4) is 40-70 DEG C, the residence time of material in phase splitter is 0.5h-2h.
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| CN201410080213.XA Active CN103787818B (en) | 2014-03-06 | 2014-03-06 | A kind of process for purification of crude sulfate turpentine |
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| 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 |
Citations (2)
| 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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Patent Citations (2)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 粗硫酸盐松节油精制研究;陈磊等;《食品和机械》;20130118;第29卷(第1期);第223-225页 * |
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