Purification equipment and purification method of alpha-terpinene

Abstract

The invention belongs to the technical field of precursor purification, and particularly relates to purification equipment and a purification method of alpha-terpinene. The purification equipment provided by the invention is simple in structure and convenient to disassemble, fill, operate and overhaul, the adsorption material can be regenerated and reused, and the operation is efficient. According to the purification equipment in the scheme, through an adsorption and rectification combined method, firstly, impurities such as eucalyptol and cymene are efficiently removed by adopting an adsorption material, and then high-boiling-point impurities, low-boiling-point impurities and ion impurities are further removed through two-stage vacuum rectification, so that a high-purity alpha-terpinene product is obtained, the product purity is 99.5% or above, and the purity of the alpha-terpinene product is higher than 99.5%. The total amount of impurities is not higher than 5ppb, the product is high in purity, high in yield and high in purification efficiency, the raw materials are easy to obtain, the cost is low, the quality is stable, and the product quality meets the downstream use requirement.

Description

Technical Field

[0001] The invention belongs to the technical field of precursor purification, and in particular relates to a purification device and a purification method for alpha-terpinene. Background Art

[0002] With the development of integrated circuits, the width and spacing of wires are constantly decreasing. The signal delay effect caused by the coupling of interconnect parasitic resistance and capacitance has become the main bottleneck restricting the improvement of chip performance. Using low-dielectric constant interlayer film materials to replace traditional SiO2 dielectrics is an effective way to reduce parasitic capacitance and interconnect delay. Diethoxymethylsilane and α-terpinene are both important low-dielectric constant interlayer film materials. The two are used in the preparation process of the insulating layer in semiconductor devices.

[0003] α-Pinpinene is a sacrificial precursor, mainly used as a pore former for chemical vapor deposition of high-quality low dielectric constant films. The purity of industrially produced α-pinpinene is about 95%, containing a large amount of compound impurities such as eucalyptol, α-phellandrene, para-cymene, α-terpenes and α-thujane, as well as non-metallic / metallic ion impurities. At present, the purification methods of α-pinpinene mainly include adsorption and extraction. Among them, the adsorption method can increase the purity of α-pinpinene to 98%, but the overall purity is still low. Summary of the invention

[0004] The purpose of the present invention is to provide a purification device and a purification method for α-terpinene. The purification method provided by the present invention can obtain α-terpinene with a purity of more than 99.5%.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a purification device for alpha-terpinene, comprising a first adsorption device, a second adsorption device, a first distillation device and a second distillation device which are connected in sequence; the first adsorption device is a first adsorption tower; the filler of the first adsorption tower is a molecular sieve; the second adsorption device is a second adsorption tower; the filler of the second adsorption tower is a phosphate compound; the first distillation device is a first distillation tower; the second distillation device is a second distillation tower; the fillers of the first distillation tower and the second distillation tower independently include one or more of stainless steel θ ring fillers, triangular spiral fillers and glass spring fillers.

[0007] Preferably, the height-to-diameter ratio of the first adsorption tower is 5 to 10:1; the filling rate of the filler in the first adsorption tower is 80 to 85%; the molecular sieve includes one or more of ZSM molecular sieve and 13X molecular sieve; the molecular sieve is activated before use; the activation temperature is 300 to 400°C, and the insulation activation time is 6 to 8h.

[0008] Preferably, the height-to-diameter ratio of the second adsorption tower is 5 to 10:1; the filling rate of the filler in the second adsorption tower is 80 to 85%; the phosphate compound includes one or more of calcium phosphate and magnesium phosphate; the purity of the phosphate compound is above 99%, the water content is less than 50 ppm, and the particle size is 3 to 5 mm.

[0009] Preferably, the height-to-diameter ratio of the first distillation tower is 5-10:1; the size of the filler in the first distillation tower is 3-5 mm×3-5 mm; and the filling rate of the filler in the first distillation tower is 80%-90%.

[0010] Preferably, the height-to-diameter ratio of the second distillation tower is 5-10:1; the size of the filler in the second distillation tower is 3-5 mm×3-5 mm; and the filling rate of the filler in the second distillation tower is 80%-90%.

[0011] Preferably, the purification equipment further comprises a storage device; and the second adsorption device is connected to the first distillation device via the storage device.

[0012] The present invention also provides a method for purifying α-terpinene using the purification device described in the above scheme, comprising the following steps:

[0013] By using the purification device described in the above scheme, the α-terpinene raw material is subjected to the first adsorption, the second adsorption, the first distillation and the second distillation in sequence to obtain α-terpinene, and the purity of the α-terpinene is above 99.5%.

[0014] Preferably, the temperature of the first adsorption is room temperature, the pressure is 10-50 kPa, and the adsorption rate is 1-3 L / min; the temperature of the second adsorption is room temperature, the pressure is 20-100 kPa, and the adsorption rate is 0.5-2 L / min.

[0015] Preferably, after the first adsorption, the first adsorption device in the purification equipment is purged; after the second adsorption, the first adsorption device and / or the second adsorption device in the purification equipment is purged.

[0016] Preferably, the first distillation is a first vacuum distillation; the tower top temperature of the first distillation is 150-175°C, and the reflux ratio is 10-15:1; the second distillation is a second vacuum distillation; the tower top temperature of the second distillation is 100-150°C, and the reflux ratio is 8-10:1.

[0017] The invention provides a purification device for alpha-terpinene. The purification device provided by the invention has a simple structure, is convenient for disassembly, loading, operation and maintenance, and the adsorption material can be regenerated and reused, and has high operation efficiency.

[0018] The present invention also provides a method for purifying α-terpinene using the purification equipment described in the above scheme. The present invention uses the purification equipment of the above scheme, and first uses an adsorption material to achieve efficient removal of impurities such as eucalyptol and p-cymene through an adsorption combined distillation method, and then further removes high and low boiling point impurities and ionic impurities through secondary vacuum distillation to obtain a high-purity α-terpinene product, the product purity is above 99.5%, the total amount of impurities is not higher than 5ppb, the product purity is high, the yield is high, the purification efficiency is high, the raw materials are easily available, the cost is low, the quality is stable, and the product quality meets the downstream use requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0020] Figure 1 The present invention provides a process flow chart of the method for purifying α-terpinene. DETAILED DESCRIPTION

[0021] The invention provides an alpha-terpinene purification device, comprising a first adsorption device, a second adsorption device, a first distillation device and a second distillation device which are connected in sequence.

[0022] The purification equipment provided by the present invention comprises a first adsorption device; the first adsorption device is preferably a first adsorption tower; the material of the first adsorption tower is preferably stainless steel; the stainless steel is preferably 316L stainless steel; the inner wall of the first adsorption tower is preferably subjected to mechanical polishing treatment.

[0023] In the present invention, the height-to-diameter ratio of the first adsorption tower is preferably 5 to 10:1, specifically 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.

[0024] In the present invention, the filler of the first adsorption tower is preferably a molecular sieve; the molecular sieve preferably includes one or more of a ZSM molecular sieve and a 13X molecular sieve; the molecular sieve is preferably activated before use; the activation temperature is preferably 300-400°C, specifically 350°C, and the insulation activation time is preferably 6-8h, specifically 7h.

[0025] In the present invention, the filling rate (volume percentage) of the filler in the first adsorption tower is preferably 80-85%, specifically 82% or 83%.

[0026] The purification equipment provided by the present invention comprises a second adsorption device; the second adsorption device is preferably a second adsorption tower; the material of the second adsorption tower is preferably stainless steel; the stainless steel is preferably 316L stainless steel; the inner wall of the second adsorption tower is preferably subjected to mechanical polishing treatment.

[0027] In the present invention, the height-to-diameter ratio of the second adsorption tower is preferably 5 to 10:1, specifically 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.

[0028] In the present invention, the filler of the second adsorption tower is preferably a phosphate compound; the phosphate compound preferably includes one or more of calcium phosphate (Ca3(PO4)2) and magnesium phosphate (Mg3(PO4)2); the purity of the phosphate compound is preferably above 99%, specifically 99% or 99.5%, the water content is preferably less than 50ppm, specifically 50ppm, 40ppm, 30ppm, 20ppm or 10ppm, and the particle size is preferably 3-5mm, specifically 3.5mm, 4mm or 4.5mm.

[0029] In the present invention, the filling rate (volume percentage) of the filler in the second adsorption tower is preferably 80-85%, specifically 82% or 83%. In the present invention, the α-terpinene raw material is passed through the first adsorption device and the second adsorption device successively to remove the chemical impurities such as eucalyptol, α-phellandrene, p-cymene, α-terpenoids and α-thujene by dynamic adsorption.

[0030] In the present invention, the second adsorption tower is preferably connected to the first adsorption tower via a first delivery pump.

[0031] The purification equipment provided by the present invention includes a first distillation device; the first distillation device is preferably a first distillation tower; the first distillation tower is preferably a first packed tower; the material of the first distillation tower is preferably stainless steel; the stainless steel is preferably 316L stainless steel; the inner wall of the first distillation tower is preferably electrolytically polished.

[0032] In the present invention, the height-to-diameter ratio of the first distillation tower is preferably 5-10:1, and specifically may be 8:1.

[0033] In the present invention, the packing of the first distillation tower preferably includes one or more of stainless steel θ ring packing, triangular spiral packing and glass spring packing, and is more preferably stainless steel θ ring packing; the size of the packing in the first distillation tower is preferably 3~5mm×3~5mm, specifically 3mm×3mm.

[0034] In the present invention, the filling rate (volume percentage) of the filler in the first distillation tower is preferably 80% to 90%, and specifically may be 85%.

[0035] In the present invention, the first distillation tower is preferably connected to the second adsorption tower via a second delivery pump.

[0036] The purification equipment provided by the present invention comprises a second distillation device; the second distillation device is preferably a second distillation tower; the second distillation tower is preferably a second packed tower; the material of the second distillation tower is preferably stainless steel; the stainless steel is preferably 316L stainless steel; the inner wall of the second distillation tower is preferably subjected to electrolytic polishing treatment.

[0037] In the present invention, the height-to-diameter ratio of the second distillation tower is preferably 5 to 10:1, and specifically may be 9:1.

[0038] In the present invention, the packing of the second distillation tower preferably includes one or more of stainless steel θ ring packing, triangular spiral packing and glass spring packing, and is more preferably stainless steel θ ring packing; the size of the packing in the second distillation tower is preferably 3~5mm×3~5mm, specifically 3mm×3mm.

[0039] In the present invention, the filling rate (volume percentage) of the filler in the second distillation tower is preferably 80% to 90%, specifically 85%.

[0040] In the present invention, the second distillation tower is preferably connected to the first distillation tower via a third delivery pump.

[0041] In the present invention, the purification device preferably further comprises a storage device; the storage device is preferably an adsorption product storage tank; the second adsorption device is preferably connected to the first distillation device via the storage device. In the present invention, after the α-pinene raw material passes through the first adsorption device and the second adsorption device, the adsorption product obtained is centrally stored in the storage device, and the adsorption product is subsequently distilled and purified to remove ionic impurities, specifically as follows Figure 1 shown.

[0042] The purification device provided by the present invention has a simple structure, is easy to disassemble, load, operate and overhaul, and the adsorption material can be regenerated and reused, so the operation is efficient.

[0043] The present invention also provides a method for purifying α-terpinene using the purification device described in the above scheme, comprising the following steps:

[0044] By using the purification device described in the above scheme, the α-terpinene raw material is subjected to the first adsorption, the second adsorption, the first distillation and the second distillation in sequence to obtain α-terpinene, and the purity of the α-terpinene is above 99.5%.

[0045] In the present invention, the purity of the α-terpinene raw material is preferably 95%. The α-terpinene raw material used in the present invention contains a large number of chemical and ionic impurities, and there are more than 30 kinds of chemical impurities, mainly eucalyptol, α-phellandrene, p-cymene, α-terpenes and α-thujene, etc., and the ionic impurities mainly include metal impurities such as Fe, Ca, Ni, Zn and Cu.

[0046] In the present invention, the temperature of the first adsorption is preferably room temperature, the pressure is preferably 10-50 kPa, specifically 20 kPa or 30 kPa, and the adsorption rate is preferably 1-3 L / min, specifically 2 L / min.

[0047] In the present invention, after the first adsorption, it is preferred that the first adsorption device in the purification equipment is purged; the purging gas is preferably nitrogen; the temperature of the nitrogen is preferably above 50°C, specifically 50°C or 80°C; the purging time is preferably above 6h, specifically 6h or 12h; the purging is preferably from top to bottom.

[0048] In the present invention, the temperature of the second adsorption is preferably room temperature, the pressure is preferably 20-100 kPa, specifically 40 kPa or 70 kPa, and the adsorption rate is preferably 0.5-2 L / min, specifically 1 L / min or 1.5 L / min.

[0049] In the present invention, after the second adsorption, it is preferred to further include purging the first adsorption device and / or the second adsorption device in the purification device; the purging gas is preferably nitrogen; the temperature of the nitrogen is preferably above 50°C, specifically 50°C or 80°C; the purging time is preferably above 6 hours, specifically 6 hours or 12 hours; the purging is preferably purged from the top to the bottom. The present invention replaces the impurities adsorbed by the filler in the adsorption device through purging, thereby ensuring the reuse of the adsorption material.

[0050] In the present invention, the first distillation is preferably a first vacuum distillation; the top temperature of the first distillation is preferably 150-175°C, specifically 155°C, 160°C, 165°C, 170°C or 175°C, the pressure is preferably -50-0kPa, specifically -50kPa, -40kPa, -30kPa, -20kPa, -10kPa or 0kPa, and the reflux ratio is preferably 10-15:1, specifically 12:1 or 13:1.

[0051] In the present invention, the second distillation is preferably a second vacuum distillation; the tower top temperature of the second distillation is preferably 100-150°C, specifically 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, the pressure is preferably -90--50kPa, specifically -50kPa, -60kPa, -70kPa, -80kPa or -90kPa, and the reflux ratio is preferably 8-10:1, specifically 9.5:1, 9:1 or 8.5:1. The present invention removes light impurities by the first distillation and removes heavy impurities by the second distillation. The present invention effectively removes metal and non-metal impurities by two-stage distillation, which has a good effect on the stability of product quality.

[0052] In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be understood as limiting the protection scope of the present invention.

[0053] Example 1

[0054] (1) The purity of the α-terpinene raw material is 95.5%. It enters the first adsorption device with a height-to-diameter ratio of 10 at a rate of 1 L / min for adsorption. The ZSM-5 molecular sieve with a size of 3 mm is filled inside, the filling rate is 82%, and the adsorption pressure is 10 kPa to obtain α-terpinene material.

[0055] (2) The α-terpinene material was introduced into a second adsorption device with a height-to-diameter ratio of 6 at a rate of 1 L / min for adsorption. The calcium phosphate with a particle size of 3 mm was filled inside, the filling rate was 82%, and the adsorption pressure was 50 kPa to obtain α-terpinene with a purity of 99.1%.

[0056] (3) The α-terpinene is uniformly stored in an adsorption product storage tank.

[0057] (4) The α-terpinene is sent to the rear-end distillation tower system: the distillation pressure of the first distillation tower is -50 kPa, the temperature is 150°C, and the reflux ratio is 10:1; the distillation pressure of the second distillation tower is -90 kPa, the temperature is 100°C, and the reflux ratio is 10:1, and the tower system parameters are controlled to be stable. After the α-terpinene is removed from the first distillation tower and the second distillation tower respectively, a high-purity α-terpinene product is obtained, with a component purity GC of 99.5% and a total impurity amount of 4.3 ppb.

[0058] Example 2

[0059] (1) The purity of the α-terpinene raw material is 95.5%. It enters the first adsorption device with a height-to-diameter ratio of 10 at a rate of 1 L / min for adsorption. The 13X molecular sieve with a size of 3 mm is filled inside, the filling rate is 80%, and the adsorption pressure is 10 kPa to obtain α-terpinene material.

[0060] (2) The α-terpinene material is introduced into a second adsorption device with a height-to-diameter ratio of 6 at a rate of 1 L / min for adsorption, and magnesium phosphate with a particle size of 3 mm is filled inside, the filling rate is 80%, and the adsorption pressure is 50 kPa to obtain α-terpinene with a purity of 99.3%.

[0061] (3) The α-terpinene is uniformly stored in an adsorption product tank.

[0062] (4) The α-terpinene is sent to the rear-end distillation tower system: the distillation pressure of the first distillation tower is -50 kPa, the temperature is 150°C, and the reflux ratio is 10:1; the distillation pressure of the second distillation tower is -90 kPa, the temperature is 100°C, and the reflux ratio is 10:1, and the tower system parameters are controlled to be stable. After the α-terpinene is removed from the first distillation tower and the second distillation tower respectively, a high-purity α-terpinene product is obtained, with a component purity GC of 99.7% and a total impurity amount of 3.6 ppb.

[0063] Example 3

[0064] (1) The purity of the α-terpinene raw material is 95.5%. It enters the first adsorption device with a height-to-diameter ratio of 10 at a rate of 1 L / min for adsorption. The ZSM-5 molecular sieve with a size of 3 mm is filled inside, the filling rate is 85%, and the adsorption pressure is 10 kPa to obtain α-terpinene material.

[0065] (2) The α-terpinene material is introduced into a second adsorption device with a height-to-diameter ratio of 6 at a rate of 1 L / min for adsorption, and magnesium phosphate with a particle size of 3 mm is filled inside, the filling rate is 85%, and the adsorption pressure is 50 kPa to obtain α-terpinene with a purity of 99.4%.

[0066] (3) The α-terpinene is uniformly stored in an adsorption product tank.

[0067] (4) The α-terpinene is sent to the rear-end distillation tower system: the distillation pressure of the first distillation tower is -50 kPa, the temperature is 150°C, and the reflux ratio is 10:1; the distillation pressure of the second distillation tower is -90 kPa, the temperature is 100°C, and the reflux ratio is 10:1, and the tower system parameters are controlled to be stable. After the α-terpinene is removed from the first distillation tower and the second distillation tower respectively, a high-purity α-terpinene product is obtained, with a component purity GC of 99.8% and a total impurity amount of 3.5 ppb.

[0068] It can be seen from the above embodiments that the purification method provided by the present invention obtains a high-purity α-terpinene product, the product purity is above 99.5%, the total amount of impurities is not higher than 5 ppb, the product purity is high, the yield is high, the purification efficiency is high, the raw materials are easily available, the cost is low, the quality is stable, and the product quality meets the downstream use requirements.

[0069] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A purification device for α-terpinene, characterized in that: It comprises a first adsorption device, a second adsorption device, a first distillation device and a second distillation device connected in sequence; the first adsorption device is a first adsorption tower; the filler of the first adsorption tower is a molecular sieve; the second adsorption device is a second adsorption tower; the filler of the second adsorption tower is a phosphate compound; the first distillation device is a first distillation tower; the second distillation device is a second distillation tower; the fillers of the first distillation tower and the second distillation tower independently comprise one or more of stainless steel θ ring fillers, triangular spiral fillers and glass spring fillers.

2. The purification device according to claim 1, characterized in that The height-to-diameter ratio of the first adsorption tower is 5 to 10:1; the filling rate of the filler in the first adsorption tower is 80 to 85%; the molecular sieve includes one or more of ZSM molecular sieve and 13X molecular sieve; the molecular sieve is activated before use; the activation temperature is 300 to 400°C, and the insulation activation time is 6 to 8 hours.

3. The purification device according to claim 1 or 2, characterized in that: The height-to-diameter ratio of the second adsorption tower is 5 to 10:1; the filling rate of the filler in the second adsorption tower is 80 to 85%; the phosphate compound includes one or more of calcium phosphate and magnesium phosphate; the purity of the phosphate compound is above 99%, the water content is less than 50 ppm, and the particle size is 3 to 5 mm.

4. The purification device according to claim 1, characterized in that The height-to-diameter ratio of the first distillation tower is 5-10:1; the size of the filler in the first distillation tower is 3-5 mm×3-5 mm; and the filling rate of the filler in the first distillation tower is 80%-90%.

5. The purification device according to claim 1 or 4, characterized in that: The height-to-diameter ratio of the second distillation tower is 5-10:1; the size of the filler in the second distillation tower is 3-5 mm×3-5 mm; and the filling rate of the filler in the second distillation tower is 80%-90%.

6. The purification device according to claim 1, characterized in that: The purification equipment further comprises a storage device; the second adsorption device is connected to the first distillation device via the storage device.

7. A method for purifying α-terpinene using the purification device described in the above scheme, characterized in that: The following steps are involved: By using the purification device according to any one of claims 1 to 6, the α-terpinene raw material is subjected to first adsorption, second adsorption, first distillation and second distillation in sequence to obtain α-terpinene, wherein the purity of the α-terpinene is above 99.5%.

8. The method according to claim 7, characterized in that The temperature of the first adsorption is room temperature, the pressure is 10-50 kPa, and the adsorption rate is 1-3 L / min; the temperature of the second adsorption is room temperature, the pressure is 20-100 kPa, and the adsorption rate is 0.5-2 L / min.

9. The method according to claim 7 or 8, characterized in that: After the first adsorption, the first adsorption device in the purification equipment is purged; after the second adsorption, the first adsorption device and / or the second adsorption device in the purification equipment is purged.

10. The method according to claim 7, characterized in that The first distillation is a first vacuum distillation; the tower top temperature of the first distillation is 150-175°C, and the reflux ratio is 10-15:1; the second distillation is a second vacuum distillation; the tower top temperature of the second distillation is 100-150°C, and the reflux ratio is 8-10:1.

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