CN113636908A - Terphenyl composition and preparation method thereof - Google Patents
Terphenyl composition and preparation method thereof Download PDFInfo
- Publication number
- CN113636908A CN113636908A CN202110931359.0A CN202110931359A CN113636908A CN 113636908 A CN113636908 A CN 113636908A CN 202110931359 A CN202110931359 A CN 202110931359A CN 113636908 A CN113636908 A CN 113636908A
- Authority
- CN
- China
- Prior art keywords
- terphenyl
- controlling
- temperature
- composition
- crude product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a refining method of a terphenyl composition, which comprises the following steps: A. preparation of crude product containing terphenyl composition: mixing and preheating raw materials of benzene and biphenyl to the temperature of 640-; B. refining of terphenyl composition: (1) adding materials; (2) reduced pressure distillation 1: heating to 160-185 ℃, collecting fractions without backflow, and discarding; (3) carrying out reduced pressure distillation 2, heating to 265-350 ℃, controlling the reflux ratio to be 3-8:1, and collecting fractions; (4) and (4) putting the collected fractions into a rectifying tower, and repeating the step (B) and the step (3) for 1-2 times to obtain the terphenyl composition. According to the preparation method provided by the invention, the terphenyl content in the prepared terphenyl composition is not lower than 93%, the biphenyl content is not higher than 2%, and the polybiphenyl content is not higher than 5%.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and relates to a terphenyl composition and a preparation method thereof.
Background
Terphenyl (C)18H14Also known as diphenylbenzene or triphenylene) is a closely related class of aromatic hydrocarbons, consisting of a central benzene ring and two phenyl substituents, with three isomers: ortho-terphenyl, meta-terphenyl, and para-terphenyl. The traditional terphenyl synthesis method is a byproduct generated by producing biphenyl from benzene, and has more high-boiling residues, the method is restricted by the production of the biphenyl, and the conversion rate is lower.
Terphenyl is a mixture of three isomers used to produce hydrogenated terphenyl. Hydrogenated terphenyl is widely applied to petrochemical industry, synthetic fibers, synthetic resins, medicine, printing and dyeing and other industries, high-temperature heat conduction and heat supply equipment systems, chemical fiber polymerization (terylene, chinlon polymerization and dry spandex spinning), organic silicon monomer synthesis, trichlorosilane, polycrystalline silicon, medicine, pesticide, dye intermediates and other fine chemical industries and biodiesel.
There is no report in the prior art of the preparation of terphenyl compositions.
Disclosure of Invention
The invention provides a preparation method of a terphenyl composition, which comprises the following steps:
A. preparation of crude product containing terphenyl composition:
the raw materials of benzene and biphenyl are quantitatively mixed and sent into a heat exchanger, the mixed raw materials are preheated to about 640-660 ℃ in the heat exchanger and enter a reaction furnace, the reaction furnace is heated to 780-820 ℃, the residence time of benzene and biphenyl steam in the reaction furnace is 2-3.5 seconds, and a crude product of the terphenyl composition is generated by reaction;
B. refining of terphenyl composition:
(1) feeding: adding a crude product containing the terphenyl composition into a rectifying tower;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 8-20 mmHg, heating the crude terphenyl product to 160-185 ℃, collecting fractions at the temperature without backflow, and discarding;
(3) carrying out reduced pressure distillation 2, controlling the vacuum degree to be 2-5 mmHg, heating the crude terphenyl product to 265-350 ℃, controlling the reflux ratio to be 3-8:1, and collecting fractions at the temperature;
(4) optionally, putting the fraction collected in the step (3) into a rectifying tower, and repeating the step B and the step (3) for 1-2 times to obtain the terphenyl composition.
In the preparation method, in the step (2) in the step B, the vacuum degree is preferably controlled to be 10-18 mmHg; more preferably 12 to 16mmHg, still more preferably 13 to 14 mmHg; more preferably 14 mmHg.
The preparation method comprises the following steps: in the step (2) in the step B, the temperature is increased to 165-180 ℃; more preferably from 170 ℃ to 175 ℃.
In the preparation method, the step (3) in the step B is; preferably, controlling the vacuum degree to be 4-5mmHg, and heating the crude product of the terphenyl to 205-210 ℃; controlling the reflux ratio to be 3-5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3-4 mmHg; heating the crude product of terphenyl to 210-215 ℃, controlling the reflux ratio to be 5-6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2-3 mmHg; heating the crude product of terphenyl to 215-220 ℃, controlling the reflux ratio to be 7-8:1, and collecting the fraction at the temperature.
Further, in the preparation method, in the step (3) in the step B, the vacuum degree is controlled to be 4-5mmHg, and the temperature of the crude terphenyl product is increased to 206-209 ℃; controlling the reflux ratio to be 3-5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3-4 mmHg; heating the crude product of terphenyl to 212-214 ℃, controlling the reflux ratio to be 5-6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2-3 mmHg; heating the crude product of terphenyl to 217-219 ℃, controlling the reflux ratio to be 7-8:1, and collecting the fraction at the temperature.
Furthermore, in the preparation method, in the step (3) in the step B, the vacuum degree is controlled to be 4-5mmHg, and the temperature of the crude terphenyl product is increased to 207-208 ℃; controlling the reflux ratio to be 4:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3-4 mmHg; heating the crude product of terphenyl to 213-214 ℃, controlling the reflux ratio to be 6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2-3 mmHg; heating the crude product of terphenyl to 217-219 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature.
Furthermore, in the crude product containing the terphenyl composition in the step A, the content of terphenyl (including ortho-terphenyl, meta-terphenyl and para-terphenyl) is not higher than 70%, the content of biphenyl is not lower than 10%, and the content of polybiphenyl is not lower than 20%.
The preparation of hydrogenated terphenyl requires that the terphenyl (including ortho-terphenyl, meta-terphenyl, para-terphenyl) content in the terphenyl composition is not less than 90%, the biphenyl content is not more than 3%, and the polybiphenyl content is not more than 7%. When the content of biphenyl in the terphenyl composition is higher than 3%, the viscosity of the prepared hydrogenated terphenyl is not in accordance with the requirement, and when the content of polybiphenyl in the terphenyl is higher than 7%, the content of polybiphenyl in the prepared hydrogenated terphenyl is higher, and the freezing point of the product is not in accordance with the requirement.
The terphenyl-containing composition prepared by the method has the terphenyl content of not less than 93 percent, the biphenyl content of not more than 2 percent and the polybiphenyl content of not more than 5 percent.
Furthermore, the terphenyl content of the composition containing the terphenyl prepared by the method is not lower than 95 percent, and the biphenyl content is not higher than 1.5 percent; the content of polybiphenyl is not higher than 4%.
Furthermore, the terphenyl content of the composition containing the terphenyl prepared by the method is not lower than 97 percent, and the biphenyl content is not higher than 1 percent; the content of polybiphenyl is not higher than 3%.
Furthermore, the terphenyl content in the composition containing the terphenyl prepared by the method is not lower than 99 percent, and the biphenyl content is not higher than 0.5 percent; the content of polybiphenyl is not higher than 1%.
The preparation method of the terphenyl composition provided by the invention has high separation yield, can separate more than 90% of terphenyl (including ortho-terphenyl, meta-terphenyl and para-terphenyl) in a crude product, and the prepared terphenyl-containing composition has the terphenyl content of not less than 93%, the biphenyl content of not more than 2% and the polybiphenyl content of not more than 5%.
Detailed Description
The invention discloses a terphenyl composition and a preparation method thereof, and the terphenyl composition can be realized by properly improving process parameters by combining the relevant principles of chemical technology by taking the contents of the invention as reference. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the invention has been described in terms of preferred embodiments, it will be apparent to those skilled in the art that variations may be applied, or changes and combinations may be made, in the methods and applications described herein to achieve and use the inventive techniques without departing from the spirit, scope, and content of the invention.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The present invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
Example 1: preparation of crude product containing terphenyl composition
The raw materials of benzene and biphenyl (the molar ratio of benzene to biphenyl is 10:1) are quantitatively mixed and sent into a heat exchanger, the mixed raw materials are preheated to about 645 ℃ and 655 ℃ in the heat exchanger and then enter a reaction furnace, the reaction furnace is heated to 790 ℃ and 810 ℃, the residence time of the benzene and biphenyl steam in the reaction furnace is 2.5 seconds, and crude product 1 containing the terphenyl composition is generated by reaction.
Example 2: preparation of crude product containing terphenyl composition
The raw materials of benzene and biphenyl (the molar ratio of benzene to biphenyl is 10:1) are quantitatively mixed and sent into a heat exchanger, the mixed raw materials are preheated to about 640-650 ℃ in the heat exchanger and then enter a reaction furnace, the reaction furnace is heated to about 780-800 ℃, the residence time of benzene and biphenyl steam in the reaction furnace is 3.5 seconds, and crude product 2 containing the terphenyl composition is generated by reaction.
Example 3: preparation of crude product containing terphenyl composition
The raw materials of benzene and biphenyl (the molar ratio of benzene to biphenyl is 10:1) are quantitatively mixed and sent into a heat exchanger, the mixed raw materials are preheated to about 650-660 ℃ in the heat exchanger and then enter a reaction furnace, the reaction furnace is heated to 800-820 ℃, the residence time of benzene and biphenyl steam in the reaction furnace is 2 seconds, and crude products 3 containing the terphenyl composition are generated by reaction.
The contents of the components of the crude terphenyl composition-containing products prepared in examples 1-3 are shown in table 1.
Table 1: crude product containing terphenyl composition and its component content table
Example 4: purification of terphenyl composition
(1) Feeding: 50Kg of crude product 1 containing a terphenyl composition is added to a rectification column;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 14mmHg, heating the crude terphenyl product to 171 ℃, collecting fractions at the temperature without reflux, and discarding;
(3) and (3) reduced pressure distillation 2: controlling the vacuum degree to be 5mmHg, and heating the crude product of the terphenyl to 208 ℃; controlling the reflux ratio to be 4:1, and collecting fractions at the temperature; controlling the vacuum degree to be 4 mmHg; heating the crude product of terphenyl to 214 ℃, controlling the reflux ratio to be 6:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 219 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature.
And (3) mixing the fractions in the step (3) to obtain 29.78Kg of terphenyl composition, wherein the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 97.1 percent, and the content and the yield of each component of the terphenyl are shown in the table 2.
Table 2: EXAMPLE 4 tables of the content and yield of each component of terphenyl composition
Example 5: purification of terphenyl composition
(1) Feeding: 50Kg of crude product 1 containing a terphenyl composition is added to a rectification column;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 13mmHg, heating the crude terphenyl product to 175 ℃, collecting fractions at the temperature without backflow, and discarding;
(3) vacuum distillation 2, controlling the vacuum degree to be 4mmHg, and heating the crude product of terphenyl to 207 ℃; controlling the reflux ratio to be 4:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 213 ℃, controlling the reflux ratio to be 6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2 mmHg; heating the crude product of terphenyl to 217 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature.
And (3) mixing the fractions in the step (3) to obtain 29.72Kg of terphenyl composition, wherein the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 97.1 percent, and the content and the yield of each component of the terphenyl are shown in the table 2.
Table 3: EXAMPLE 5 terphenyl composition Components and yield Table
Example 6: purification of terphenyl composition
The procedures (1), (2) and (3) are the same as those in example 4.
(4) Putting the fraction collected in the step (3) into a rectifying tower, repeating the step (3) for 1 time to obtain 29.28Kg of terphenyl composition, wherein the content of terphenyl (including ortho-terphenyl, meta-terphenyl and para-terphenyl) is 99.4 percent, and the content and the yield of each component of the terphenyl are shown in Table 4.
Table 4: EXAMPLE 6 terphenyl composition Components and yield Table
Example 7: purification of terphenyl composition
The procedures (1), (2) and (3) were the same as in example 5.
(4) Putting the fraction collected in the step (3) into a rectifying tower, repeating the step (3) for 1 time to obtain 29.25Kg of terphenyl composition, wherein the content of terphenyl (including ortho-terphenyl, meta-terphenyl and para-terphenyl) is 99.2 percent, and the content and the yield of each component of the terphenyl are shown in Table 5.
Table 5: EXAMPLE 7 terphenyl compositions Components and yield Table
Example 8: purification of terphenyl composition
(1) Feeding: 50Kg of crude product 1 containing a terphenyl composition is added to a rectification column;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 12mmHg, heating the crude terphenyl product to 168 ℃, collecting fractions at the temperature without backflow, and discarding;
(3) reduced pressure distillation 2: firstly, controlling the vacuum degree to be 5mmHg, and heating the crude product of terphenyl to 209 ℃; controlling the reflux ratio to be 3:1, and collecting fractions at the temperature; controlling the vacuum degree to be 4 mmHg; heating the crude product of terphenyl to 214 ℃, controlling the reflux ratio to be 6:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 219 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature.
And (3) mixing the fractions in the step (3) to obtain 29.63Kg of terphenyl composition, wherein the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 95.4 percent, and the content and the yield of each component of the terphenyl are shown in Table 6.
Table 6: EXAMPLE 8 terphenyl composition Components and yield Table
Example 9: purification of terphenyl composition
(1) Feeding: 50Kg of crude product 1 containing a terphenyl composition is added to a rectification column;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 16mmHg, heating the crude terphenyl product to 178 ℃, collecting fractions at the temperature without backflow, and discarding;
(3) vacuum distillation 2, controlling the vacuum degree to be 4mmHg, and heating the crude product of the terphenyl to 206 ℃; controlling the reflux ratio to be 5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 212 ℃, controlling the reflux ratio to be 5:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2 mmHg; heating the crude product of terphenyl to 217 ℃, controlling the reflux ratio to be 7:1, and collecting the fraction at the temperature.
And (3) mixing the fractions in the step (3) to obtain 30.03Kg of terphenyl composition, wherein the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 95.0 percent, and the content and the yield of each component of the terphenyl are shown in the table 7.
Table 7: EXAMPLE 9 terphenyl compositions Components content and yield Table
Example 10: purification of terphenyl composition
(1) Feeding: 50Kg of crude product 1 containing a terphenyl composition is added to a rectification column;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 10mmHg, heating the crude terphenyl product to 165 ℃, collecting fractions at the temperature without backflow, and discarding;
(3) reduced pressure distillation 2: firstly, controlling the vacuum degree to be 5mmHg, and heating the crude product of terphenyl to 205 ℃; controlling the reflux ratio to be 3:1, and collecting fractions at the temperature; controlling the vacuum degree to be 4 mmHg; heating the crude product of terphenyl to 210 ℃, controlling the reflux ratio to be 5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 2 mmHg; heating the crude product of terphenyl to 215 ℃, controlling the reflux ratio to be 7:1, and collecting the fraction at the temperature.
And (3) mixing the fractions in the step (3) to obtain 30.38Kg of terphenyl composition, wherein the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 93.4 percent, and the content and the yield of each component of the terphenyl are shown in a table 8.
Table 8: EXAMPLE 10 terphenyl composition Components content and yield Table
Example 11: purification of terphenyl composition
(1) Feeding: 50Kg of crude product 1 containing a terphenyl composition is added to a rectification column;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 18mmHg, heating the crude terphenyl product to 180 ℃, collecting fractions at the temperature without backflow, and discarding;
(3) vacuum distillation 2, controlling the vacuum degree to be 4mmHg, and heating the crude product of the terphenyl to 210 ℃; controlling the reflux ratio to be 5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 215 ℃, controlling the reflux ratio to be 6:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 220 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature.
And (3) mixing the fractions in the step (3) to obtain 30.47Kg of terphenyl composition, wherein the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 93.6 percent, and the content and the yield of each component of the terphenyl are shown in a table 9.
Table 9: EXAMPLE 11 ingredient content and yield Table of terphenyl composition
Example 12: purification of terphenyl composition
(1) Feeding: adding 50Kg of crude product 2 containing the terphenyl composition into a rectifying tower;
the steps (2) and (3) are the same as in example 7.
29.90Kg of terphenyl composition is obtained, the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 97.1 percent, and the content and the yield of each component of the terphenyl are shown in Table 11.
Table 10: EXAMPLE 12 ingredient content and yield of terphenyl composition
Example 13: purification of terphenyl composition
(1) Feeding: adding 50Kg of crude product 3 containing terphenyl composition into a rectifying tower;
the steps (2) and (3) are the same as in example 7.
30.47Kg of terphenyl composition is obtained, the content of terphenyl (including o-terphenyl, m-terphenyl and p-terphenyl) is 97.0 percent, and the content and the yield of each component of the terphenyl are shown in Table 11.
Table 11: EXAMPLE 13 terphenyl composition Components and yield Table
Comparative example 1: influence of the step (2) in the step B on the content and yield of the prepared terphenyl composition
The procedure (1) and (3) were the same as in example 7, and the procedure (2) was as follows.
Comparative example 1-1 preparation method: step (2) is omitted.
Comparative examples 1-2 preparation methods: step (2): reduced pressure distillation 1: controlling the vacuum degree to be 14mmHg, heating the crude terphenyl product to 155 ℃, collecting fractions at the temperature without reflux, and discarding the fractions.
Comparative examples 1 to 3 preparation methods: step (2): reduced pressure distillation 1: controlling the vacuum degree to be 14mmHg, heating the crude terphenyl product to 190 ℃, collecting fractions at the temperature without reflux, and discarding the fractions.
The contents of the respective components and the yields of the terphenyl composition prepared in comparative example 1 are shown in table 12.
Table 12: comparative example 1 terphenyl composition content and yield table
Comparing Table 12 with tables 2-11, it can be seen that: the content of the terphenyl composition obtained by preparation and the yield of each component are influenced by the step (2) in the step B; when the step (2) in the step B is omitted in the preparation method (as in a comparative example 1-1), the biphenyl content in the prepared terphenyl is obviously increased to 17 percent and is not in line with the requirement; when the temperature of the step B is lower than 160 ℃ (as in the comparative example 1-2), the biphenyl content in the prepared terphenyl is increased to 7.5%, and the terphenyl does not meet the requirement; ③ when the temperature in the step (2) in the step (B) is higher than 185 ℃ (as in the comparative examples 1-3), the yield of the o-terphenyl in the prepared terphenyl is lower and is 72.4 percent. Step B should therefore be "(2) distillation under reduced pressure 1: controlling the vacuum degree to be 8-20 mmHg, heating the crude product of the terphenyl to 160-185 ℃, collecting fractions at the temperature without backflow, and discarding the fractions.
Comparative example 2: influence of the step (3) in the step B on the content and yield of the prepared terphenyl composition
The procedure (1) and (2) were the same as in example 7, and the procedure (3) was as follows.
Comparative example 2-1 preparation method: step (3), reduced pressure distillation 2: firstly, controlling the vacuum degree to be 5mmHg, and heating the crude product of terphenyl to 212 ℃; controlling the reflux ratio to be 4:1, and collecting fractions at the temperature; controlling the vacuum degree to be 4 mmHg; heating the crude product of terphenyl to 217 ℃, controlling the reflux ratio to be 6:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 225 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature.
Comparative example 2-2 preparation method: : step (3), reduced pressure distillation 2: firstly, controlling the vacuum degree to be 8mmHg, and heating the crude product of the terphenyl to 208 ℃; controlling the reflux ratio to be 4:1, and collecting fractions at the temperature; controlling the vacuum degree to be 6 mmHg; heating the crude product of terphenyl to 214 ℃, controlling the reflux ratio to be 6:1, and collecting fractions at the temperature; controlling the vacuum degree to be 5 mmHg; heating the crude product of terphenyl to 219 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature. (high biphenyl content, low yield of three biphenyls)
Comparative examples 2 to 3 preparation method: step (3), reduced pressure distillation 2: controlling the vacuum degree to be 5mmHg, and heating the crude product of the terphenyl to 208 ℃; controlling the reflux ratio to be 2:1, and collecting fractions at the temperature; controlling the vacuum degree to be 4 mmHg; heating the crude product of terphenyl to 214 ℃, controlling the reflux ratio to be 3:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3 mmHg; heating the crude product of terphenyl to 219 ℃, controlling the reflux ratio to be 4:1, and collecting the fraction at the temperature.
The content and yield of each component of the terphenyl composition prepared in comparative example 2 are shown in table 13.
Table 13: comparative example 2 terphenyl composition ingredient content and yield table
Comparing Table 13 with tables 2-11, it can be seen that: the content of the terphenyl composition obtained by preparation and the yield of each component are influenced by the step (3) in the step B; when the temperature of the step (3) in the step B is higher (as in a comparative example 2-1), the content of polybiphenyl in the prepared terphenyl is obviously increased to 8.5 percent, the terphenyl does not meet the requirement, and the yield of the ortho-terphenyl is lower and is only 66.9 percent; secondly, when the vacuum degree in the step (3) in the step B is larger (as a comparative example 2-2), the biphenyl content in the prepared terphenyl is higher and reaches 3.5 percent, the terphenyl does not meet the requirement, and the yields of the ortho-terphenyl, the meta-terphenyl and the para-terphenyl are lower and lower than 80 percent; and thirdly, when the reflux ratio in the step (3) in the step B is smaller (as in a comparative example 2-3), the content of the polybiphenyl in the prepared terphenyl is obviously increased and reaches 7.1 percent, and the terphenyl does not meet the requirement. Therefore, in the step (3), firstly, controlling the vacuum degree to be 4-5mmHg, and heating the crude product of the terphenyl to 205-210 ℃; controlling the reflux ratio to be 3-5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3-4 mmHg; heating the crude product of terphenyl to 210-215 ℃, controlling the reflux ratio to be 5-6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2-3 mmHg; heating the crude product of terphenyl to 215-220 ℃, controlling the reflux ratio to be 7-8:1, and collecting the fraction at the temperature.
Claims (8)
1. A preparation method of a terphenyl composition is characterized by comprising the following steps:
A. preparation of crude product containing terphenyl composition:
the raw materials of benzene and biphenyl are quantitatively mixed and sent into a heat exchanger, the mixed raw materials are preheated to about 640-660 ℃ in the heat exchanger and enter a reaction furnace, the reaction furnace is heated to 780-820 ℃, the residence time of benzene and biphenyl steam in the reaction furnace is 2-3.5 seconds, and a crude product of the terphenyl composition is generated by reaction;
B. refining of terphenyl composition:
(1) feeding: adding a crude product containing the terphenyl composition into a rectifying tower;
(2) reduced pressure distillation 1: controlling the vacuum degree to be 8-20 mmHg, heating the crude terphenyl product to 160-185 ℃, collecting fractions at the temperature without backflow, and discarding;
(3) carrying out reduced pressure distillation 2, controlling the vacuum degree to be 2-5 mmHg, heating the crude terphenyl product to 265-350 ℃, controlling the reflux ratio to be 3-8:1, and collecting fractions at the temperature;
(4) optionally, putting the fraction collected in the step C into a rectifying tower, and repeating the step B and the step C for 1-2 times to obtain the terphenyl composition.
2. The refining method according to claim 1, wherein in the step (2) of B, the degree of vacuum is controlled to 10 to 18 mmHg.
3. The refining method according to claim 1, wherein in the step (2) of B, the degree of vacuum is controlled to 12 to 16 mmHg.
4. The refining method according to claim 1, wherein in the step (2) of B, the degree of vacuum is controlled to be 13 to 14 mmHg.
5. The refining method of claim 1, wherein in the step B, the temperature is raised to 165-180 ℃.
6. The refining process of any one of claims 1 to 5, wherein step (3) in step B is; preferably, controlling the vacuum degree to be 4-5mmHg, and heating the crude product of the terphenyl to 205-210 ℃; controlling the reflux ratio to be 3-5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3-4 mmHg; heating the crude product of terphenyl to 210-215 ℃, controlling the reflux ratio to be 5-6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2-3 mmHg; heating the crude product of terphenyl to 215-220 ℃, controlling the reflux ratio to be 7-8:1, and collecting the fraction at the temperature.
7. The refining method of claim 6, wherein in the step (3) of B, the vacuum degree is controlled to be 4-5mmHg, and the temperature of the crude terphenyl is increased to 206-209 ℃; controlling the reflux ratio to be 3-5:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3-4 mmHg; heating the crude product of terphenyl to 212-214 ℃, controlling the reflux ratio to be 5-6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2-3 mmHg; heating the crude product of terphenyl to 217-219 ℃, controlling the reflux ratio to be 7-8:1, and collecting the fraction at the temperature.
8. The refining method of claim 6, wherein in the step (3) of B, the vacuum degree is controlled to be 4-5mmHg, and the temperature of the crude terphenyl is increased to 207-208 ℃; controlling the reflux ratio to be 4:1, and collecting fractions at the temperature; controlling the vacuum degree to be 3-4 mmHg; heating the crude product of terphenyl to 213-214 ℃, controlling the reflux ratio to be 6:1, and collecting the fraction at the temperature; controlling the vacuum degree to be 2-3 mmHg; heating the crude product of terphenyl to 217-219 ℃, controlling the reflux ratio to be 8:1, and collecting the fraction at the temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110931359.0A CN113636908A (en) | 2021-08-13 | 2021-08-13 | Terphenyl composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110931359.0A CN113636908A (en) | 2021-08-13 | 2021-08-13 | Terphenyl composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113636908A true CN113636908A (en) | 2021-11-12 |
Family
ID=78421519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110931359.0A Pending CN113636908A (en) | 2021-08-13 | 2021-08-13 | Terphenyl composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113636908A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032076A (en) * | 2021-12-27 | 2022-02-11 | 涉县津东经贸有限责任公司 | Hydrogenated terphenyl heat conduction oil synthesis process |
| CN114149299A (en) * | 2021-12-08 | 2022-03-08 | 涉县津东经贸有限责任公司 | Preparation method of biphenyl |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB953140A (en) * | 1960-12-10 | 1964-03-25 | Progil | Improvements in the manufacture of terphenyls from benzene |
| GB957065A (en) * | 1960-07-22 | 1964-05-06 | Bayer Ag | Process for the production of terphenyl |
| DE1272281B (en) * | 1961-01-18 | 1968-07-11 | Progil | Process for the preparation of mixtures containing o-, m- and p-terphenyl isomers |
| CN103804114A (en) * | 2013-12-05 | 2014-05-21 | 安徽奥瑞化工有限公司 | Method for preparing hydrogenated terphenyl |
| CN205517715U (en) * | 2016-02-05 | 2016-08-31 | 涉县津东经贸有限责任公司 | Energy -conserving tubular terphenyl reaction apparatus for producing |
| CN109053355A (en) * | 2018-09-29 | 2018-12-21 | 上海化工研究院有限公司 | A kind of method of continuous rectification biphenyl purification |
-
2021
- 2021-08-13 CN CN202110931359.0A patent/CN113636908A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB957065A (en) * | 1960-07-22 | 1964-05-06 | Bayer Ag | Process for the production of terphenyl |
| GB953140A (en) * | 1960-12-10 | 1964-03-25 | Progil | Improvements in the manufacture of terphenyls from benzene |
| DE1272281B (en) * | 1961-01-18 | 1968-07-11 | Progil | Process for the preparation of mixtures containing o-, m- and p-terphenyl isomers |
| CN103804114A (en) * | 2013-12-05 | 2014-05-21 | 安徽奥瑞化工有限公司 | Method for preparing hydrogenated terphenyl |
| CN205517715U (en) * | 2016-02-05 | 2016-08-31 | 涉县津东经贸有限责任公司 | Energy -conserving tubular terphenyl reaction apparatus for producing |
| CN109053355A (en) * | 2018-09-29 | 2018-12-21 | 上海化工研究院有限公司 | A kind of method of continuous rectification biphenyl purification |
Non-Patent Citations (1)
| Title |
|---|
| 李云飞等主编: "《食品工程原理》", 31 August 2018, 中国农业大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149299A (en) * | 2021-12-08 | 2022-03-08 | 涉县津东经贸有限责任公司 | Preparation method of biphenyl |
| CN114032076A (en) * | 2021-12-27 | 2022-02-11 | 涉县津东经贸有限责任公司 | Hydrogenated terphenyl heat conduction oil synthesis process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113636908A (en) | Terphenyl composition and preparation method thereof | |
| CN109665934B (en) | Method for preparing dicyclopentadiene | |
| CN103232317A (en) | Aromatic hydrocarbon purification apparatus and process used in hydrofining of coking crude benzene | |
| CN102336622B (en) | Reclaiming device and separation method for heavy component residue of coked crude benzene hydrogenation process | |
| CN101220124B (en) | Process for preparing decyclization C5 hydrogenation resin | |
| KR101811676B1 (en) | Purification device for naphtha and purification method for naphtha using the same | |
| CN104276912A (en) | Method for separating byproducts C9-C10 fractions in ethylene preparation through petroleum cracking and increasing yield | |
| CN100494131C (en) | Method for recovering benzene and toluene | |
| CN114292155B (en) | Method for purifying mesitylene through thermal coupling | |
| CN109704907A (en) | It raffinates oil the method for preparing hexane | |
| CN107445786B (en) | Method for preparing biphenyl by hydrogenation of dibenzofuran | |
| CN109867580A (en) | From the method and apparatus for adding hydrogen Residual oil aromatics separation solvent naphtha and naphthalene Related product | |
| CN104276914A (en) | Method for separating by-product C9-C10 fractions in ethylene preparation through petroleum cracking by using rectifying tower | |
| CN108586199B (en) | Method for extracting and separating terpineol from eucalyptus volatile oil | |
| CN108864126B (en) | Method for continuously and hierarchically rectifying eucalyptus oil | |
| US3719718A (en) | Process for the production of cyclopentadiene from dicyclopentadiene | |
| EP4007747B1 (en) | Recovery of isoprene and cpd from a pygas stream | |
| CN110698318A (en) | Production method of high-purity cyclopentene | |
| DE60105451T2 (en) | PROCESS FOR REMOVING REACTIVE INJECTION PRODUCTS FROM THE EXPIRY OF SELECTIVE HYDROGENATION | |
| CN114149299B (en) | Preparation method of biphenyl | |
| CN216972386U (en) | System for aniline purification | |
| JPS622566B2 (en) | ||
| CN112174997B (en) | Device and method for preparing high-purity gamma-chloropropyltrichlorosilane | |
| CN203159507U (en) | Aromatic hydrocarbon purifying device for coking crude benzene hydrofining | |
| CN104276919B (en) | By the separation method of petroleum cracking Crude products.deep process C9~C10 cuts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |