CN116023911A - Hydrogenated terphenyl type high-temperature heat conduction oil and preparation method thereof - Google Patents
Hydrogenated terphenyl type high-temperature heat conduction oil and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of heat conduction oil, and discloses hydrogenated terphenyl type high-temperature heat conduction oil and a preparation method thereof. The heat conduction oil contains: dicyclohexylbenzene, cyclohexylbiphenyl and terphenyl, and the content of cyclohexylbiphenyl in the heat transfer oil is not less than 40 wt%. The invention adopts the solid acid catalyst to carry out alkylation reaction between the cyclohexylbenzene and cyclohexene and/or cyclohexanol, and then carries out partial dehydrogenation reaction through the dehydrogenation catalyst after separation, so that the yield of hydrogenated terphenyl is high, the preparation process is simple, the energy consumption is low, the stability is good, and the product meets the corresponding requirements in national standard regulation.
Description
Technical Field
The invention relates to the field of heat conduction oil, in particular to hydrogenated terphenyl type high-temperature heat conduction oil and a preparation method thereof.
Background
Hydrogenated terphenyl is widely applied to industries such as petroleum and petrochemical industry, chemical fiber, papermaking, textile, food, solar photo-thermal and the like as a synthetic high-temperature heat carrier. In the prior art, the preparation method of hydrogenated terphenyl usually adopts raw material benzene to obtain terphenyl after high-temperature condensation; the mixture obtained after the partial hydrogenation of the terphenyl is the desired hydrogenated terphenyl heat transfer oil, and the terphenyl in the terphenyl is by-produced from biphenyl, so that the yield of the terphenyl determines the economy and the energy and material consumption of the benzene process. Terphenyl is used as a byproduct in the process, the yield is low, and the energy consumption of the whole route is high. In recent years, with the large investment of photovoltaic power generation and air energy storage, the market demand for hydrogenated terphenyl type high-temperature heat conduction oil is increasing, so that a new technology with low energy consumption is developed, the yield of hydrogenated terphenyl is improved, and the hydrogenated terphenyl heat conduction oil with high thermal stability is prepared, so that the hydrogenated terphenyl type high-temperature heat conduction oil has important significance for wider application of the hydrogenated terphenyl type high-temperature heat conduction oil.
Disclosure of Invention
The invention aims to solve the problems of low yield, high preparation energy consumption and poor thermal stability of products of hydrogenated terphenyl in the prior art, and provides hydrogenated terphenyl heat conduction oil and a preparation method thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a hydrogenated terphenyl type high temperature heat conductive oil comprising: dicyclohexylbenzene, cyclohexylbiphenyl and terphenyl, and the content of cyclohexylbiphenyl in the heat transfer oil is not less than 40 wt%.
The invention also provides a preparation method of the hydrogenated terphenyl type high-temperature heat conduction oil, which comprises the following steps:
(1) Carrying out alkylation reaction on cyclohexylbenzene and cyclohexene and/or cyclohexanol under the action of a solid acid catalyst to generate a mixture containing dicyclohexylbenzene;
(2) Removing the C6-C12 component from the dicyclohexylbenzene-containing mixture to obtain dicyclohexylbenzene;
(3) And (3) partially dehydrogenating dicyclohexylbenzene under the action of a dehydrogenation catalyst to obtain hydrogenated terphenyl type high-temperature heat conduction oil.
The invention adopts the solid acid catalyst to carry out alkylation reaction between the cyclohexylbenzene and cyclohexene and/or cyclohexanol, and then carries out partial dehydrogenation reaction through the dehydrogenation catalyst after separation, so that the yield of hydrogenated terphenyl is high, the energy consumption in the preparation process is low, and the product meets the corresponding requirements in national standard regulation.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In one aspect, the present invention provides a hydrogenated terphenyl type high temperature heat transfer oil comprising: dicyclohexylbenzene, cyclohexylbiphenyl and terphenyl, and the content of cyclohexylbiphenyl in the heat transfer oil is not less than 40 wt%.
According to a preferred embodiment of the present invention, the total amount of dicyclohexylbenzene, cyclohexylbiphenyl and terphenyl in the hydrogenated terphenyl type high temperature heat conductive oil is not less than 70 wt%, preferably not less than 80 wt%.
According to a preferred embodiment of the present invention, the content of the cyclohexylbiphenyl is not less than 45% by weight, preferably 45 to 55% by weight. The adoption of the preferred embodiment is more beneficial to improving the thermal oxidation stability of the components in the product and prolonging the service life of the components.
According to a preferred embodiment of the present invention, the content of dicyclohexylbenzene in the heat transfer oil is 5-60 wt%, the content of cyclohexylbiphenyl is 40-80 wt%, and the content of terphenyl is 1-30 wt%; further preferably, the content of dicyclohexylbenzene in the heat conduction oil is 10-40 wt%, the content of cyclohexylbiphenyl is 45-55 wt%, and the content of terphenyl is 5-20 wt%. The hydrogenated terphenyl high-temperature heat conduction oil disclosed by the invention preferably contains higher content of cyclohexyl biphenyl, and preferably contains specific amounts of dicyclohexylbenzene, cyclohexyl biphenyl and terphenyl, so that the product composition is richer, and the hydrogenated terphenyl heat conduction oil has the advantages of low pour point, good thermal stability and low deterioration rate due to multi-component matching.
According to the present invention, the conduction oil satisfying the aforementioned requirements can be used in the present invention, and there is no particular requirement on the source of each of the components, and for the present invention, it is preferable that the dicyclohexylbenzene comes from the alkylation reaction of cyclohexylbenzene with cyclohexene and/or cyclohexanol; preferably, the cyclohexylbiphenyl and terphenyl are derived from the dehydrogenation of dicyclohexylbenzene. The preferred embodiment can effectively reduce energy consumption, so that the hydrogenated terphenyl heat conduction oil has the advantages of wide source and low cost.
The invention also provides a preparation method of the hydrogenated terphenyl type high-temperature heat conduction oil, which comprises the following steps:
(1) Carrying out alkylation reaction on cyclohexylbenzene and cyclohexene and/or cyclohexanol under the action of a solid acid catalyst to generate a mixture containing dicyclohexylbenzene;
(2) Removing the C6-C12 component from the dicyclohexylbenzene-containing mixture to obtain dicyclohexylbenzene;
(3) And (3) partially dehydrogenating dicyclohexylbenzene under the action of a dehydrogenation catalyst to obtain hydrogenated terphenyl type high-temperature heat conduction oil.
The invention adopts the solid acid catalyst to carry out alkylation reaction on the cyclohexylbenzene and cyclohexene and/or cyclohexanol, and then carries out dehydrogenation reaction through the dehydrogenation catalyst after separation, so that the yield of hydrogenated terphenyl is high.
According to the present invention, preferably, the solid acid catalyst comprises a mesoporous molecular sieve and/or a heteropolyacid and a binder.
In the present invention, the object of the present invention can be achieved by using a mesoporous molecular sieve and/or a heteropolyacid in the solid acid catalyst, preferably the solid acid catalyst comprises a mesoporous molecular sieve having acidity, a heteropolyacid and a binder. The adoption of the preferred embodiment is more beneficial to alkylation reaction between cyclohexylbenzene molecules and cyclohexene/cyclohexanol, improves the diffusion of macromolecules of reaction products, and avoids the deactivation of the catalyst caused by excessive carbon deposition.
According to the invention, the mesoporous molecular sieve is preferably a MWW, FAU, BEA mesoporous molecular sieve, and specifically can be at least one selected from a mesoporous MWW-22 molecular sieve, a mesoporous Y-type molecular sieve and a mesoporous beta molecular sieve, and is further preferably a mesoporous MWW-22 molecular sieve and/or a mesoporous Y-type molecular sieve. The molecular sieve raw powder MWW-22, beta and Y molecular sieves used in the invention are all from commercial purchase and can also be synthesized in a laboratory. The mesoporous MWW molecular sieve and the mesoporous beta molecular sieve are obtained by adopting an alkali treatment method; the mesoporous Y-type molecular sieve is obtained by a hydrothermal treatment method, and an alkali treatment method or a hydrothermal treatment method is adopted, belongs to a conventional technical means in the field of molecular sieves, and does not need to be specifically described. For example, the mesoporous MWW and mesoporous beta molecular sieves have a silica to alumina ratio of between 30 and 40 and a mesoporous volume of between 0.2 and 0.4cm 3 /g; the mesoporous Y molecular sieve has a silicon-aluminum ratio of 10-20 and a mesoporous volume of 0.2-0.4cm 3 And/g. The use of such preferred embodiments is more advantageous in improving the reactivity and diffusivity of the molecular sieve.
According to the present invention, it is preferable that the heteropolyacid is a phosphotungstic acid type heteropolyacid, particularly preferably, the heteropolyacid is selected from phosphomolybdic acid and/or phosphotungstic acid, further preferably, phosphotungstic acid. The solid acid catalyst prepared by phosphotungstic acid has higher cyclohexene conversion rate and dicyclohexylbenzene selectivity in the alkylation reaction of cyclohexylbenzene and cyclohexene, and is further beneficial to improving the yield of hydrogenated terphenyl.
According to the present invention, the binder is widely selected, and preferably, the binder is at least one selected from alumina, silica, clay and diatomaceous earth, and more preferably, alumina.
According to the present invention, it is preferable that the content of the mesoporous molecular sieve and/or heteropolyacid is 50 to 70% by weight, the content of the binder is 30 to 50% by weight, more preferably, the content of the mesoporous molecular sieve and/or heteropolyacid is 60 to 70% by weight, and the content of the binder is 30 to 40% by weight, based on the total amount of the solid acid catalyst.
The method for producing the solid acid catalyst according to the present invention is not particularly limited as long as the above-mentioned alkylation reaction can be performed, and any method known in the art may be used.
According to a preferred embodiment of the present invention, when the solid acid catalyst comprises a mesoporous molecular sieve and a binder, the solid acid catalyst preparation method comprises: kneading the mesoporous molecular sieve and a binder to form, and then drying and roasting; and finally, carrying out ammonium exchange on the product obtained by roasting. The drying, calcination and ammonium exchange may all be carried out according to conventional conditions. Preferably, the drying comprises: drying at 100-150deg.C for 5-24 hr. Preferably, the firing includes: roasting at 450-650 deg.c for 3-8 hr. Preferably, the ammonium exchange comprises: exchanging the product obtained by roasting with ammonium salt solution for 1-24 hours at 40-100 ℃, washing with deionized water, drying for 5-24 hours at 100-150 ℃ and roasting for 3-8 hours at 450-650 ℃. Preferably, the ammonium salt solution comprises an aqueous solution prepared by mixing one or any two of ammonium nitrate, ammonium chloride, ammonium sulfate and ammonium oxalate with deionized water. In the preparation process of the solid acid catalyst, the molded sample can be dried for 1-24 hours at normal temperature and normal pressure before being dried.
According to a preferred embodiment of the present invention, when the solid acid catalyst comprises a heteropolyacid and a binder, the solid acid catalyst preparation method comprises: the heteropoly acid is kneaded with a binder to be molded, and then dried and baked. Preferably, the drying comprises: drying at 100-150deg.C for 5-24 hr. Preferably, the firing includes: roasting at 350-550 deg.c for 3-8 hr. In the preparation process of the solid acid catalyst, the molded sample can be dried for 1-24 hours at normal temperature and normal pressure before being dried.
According to the invention, the solid acid catalyst may take on any physical form, such as powder, granules or molded articles, such as spheres, flakes, strips, clover; preferably spherical or bar-shaped. These physical forms may be obtained in any manner conventionally known in the art, and are not particularly limited.
In the preparation of hydrogenated terphenyl heat transfer oil according to the present invention, preferably, the alkylation reaction conditions include: the reaction temperature is 80-200 ℃, the reaction pressure is 0.8-3.0MPa, and the molar ratio of the cyclohexylbenzene to the cyclohexene and/or cyclohexanol is 1-6:1, cyclohexene and/or cyclohexanol mass space velocity of 0.1-2.0h -1 . Specifically, as the reaction temperature, for example, 150 to 190 ℃ may be preferable; as the reaction pressure, for example, 1.0 to 2.5MPa can be preferable; as the molar ratio of cyclohexylbenzene to cyclohexene and/or cyclohexanol, for example, 2 to 5 may be preferred: 1, a step of; as said cyclohexene and/or cyclohexanol mass space velocity, 0.8 to 1.5h may be preferred -1 。
According to the present invention, the method for removing the C6-C12 component in the dicyclohexylbenzene-containing mixture in the step (2) is not particularly limited, and preferably the C6-C12 component in the dicyclohexylbenzene-containing mixture is removed by distillation under reduced pressure. Wherein the C6-C12 component mainly comprises cyclohexene/cyclohexanol and cyclohexylbenzene, and a small amount of methylcyclopentane and the like.
According to a preferred embodiment of the present invention, the conditions of the reduced pressure distillation include: the temperature is 220-300 ℃ and the vacuum degree is 2-10kPa. Specifically, as the temperature, for example, 240 to 290 ℃ may be preferable; as the vacuum degree, for example, 3 to 5kPa may be preferable.
According to the present invention, the range of choice for the dehydrogenation catalyst is wide, as long as dehydrogenation of dicyclohexylbenzene can be achieved. Preferably, the dehydrogenation catalyst comprises a support and a dehydrogenation metal.
According to a preferred embodiment of the present invention, the support is selected from at least one of alumina, silica.
According to a preferred embodiment of the invention, the dehydrogenation metal is selected from at least one of a group VIII non-noble metal and/or at least one of a noble metal having the meaning conventional in the art, the noble metal being selected from at least one of gold, silver and platinum group metals (ruthenium, rhodium, palladium, osmium, iridium, platinum). Further, the dehydrogenation metal may preferably be at least one of Ni, pt, and Pd.
According to a preferred embodiment of the present invention, the dehydrogenation catalyst comprises 85 to 99 wt% of the carrier and 1 to 15 wt% of the dehydrogenation metal, based on the total amount of the dehydrogenation catalyst. Further preferably, the carrier is present in an amount of 87 to 98 wt% and the dehydrogenation metal is present in an amount of 2 to 13 wt% based on the total amount of dehydrogenation catalyst.
The method for producing the dehydrogenation catalyst is not particularly limited, and may be, for example, a conventional impregnation method. The specific preferred method comprises the following steps: the metal active component is loaded on the alumina carrier in the form of precursor salt solution, and is dried for 1-24 hours at normal temperature and normal pressure optionally, and then is dried and roasted. The drying preferably comprises: drying at 100-150 ℃ for 5-24 hours, said firing preferably comprising: roasting for 3-8 hours at 450-650 ℃. The dehydrogenation catalyst further comprises, prior to use, reducing it, preferably comprising: under the hydrogen atmosphere, the reduction temperature is 100-500 ℃, the reduction time is 0.5-12 hours, and the hydrogen volume airspeed is 100-600 hours -1 . The precursor salt may be at least one of water-soluble compounds corresponding to the dehydrogenated metal, and the present invention is not particularly limited thereto, and one skilled in the art may appropriately select the precursor salt.
According to a preferred embodiment of the present invention, the dehydrogenation catalyst may take any physical form, such as powder, granules or molded articles, such as spheres, flakes, strips, clover; preferably spherical, bar-shaped. These physical forms may be obtained in any manner conventionally known in the art, and are not particularly limited.
According to a preferred embodiment of the present invention, the conditions for the partial dehydrogenation comprise: the reaction temperature is 300-450 ℃, the molar ratio of hydrogen to dicyclohexylbenzene is 0.1-30, and the mass airspeed of dicyclohexylbenzene is 0.1-2.0h -1 . Specifically, as the reaction temperature, for example, 320 to 400 ℃ may be preferable; as the molar ratio of the hydrogen to dicyclohexylbenzene, it may be preferably 0.5 to 20:1, under the preferable conditions, the catalyst life is improved, and the rapid carbon deposition deactivation of the catalyst is prevented. As the dicyclohexylbenzene mass space velocity, 0.8 to 1.5 hours may be preferable -1 。
The hydrogenated terphenyl heat conduction oil provided by the invention has the advantages of simple preparation process, low energy consumption, small product composition difference and good stability in actual industrial production, can be used for obtaining hydrogenated terphenyl heat conduction oil with excellent high temperature resistance, and can replace the traditional hydrogenated terphenyl product.
The following examples illustrate the advantages of the present invention in detail, but are not limited to the scope of the invention.
The following preparation examples are presented to illustrate the preparation of solid acid catalysts
The molecular sieve raw powder MWW-22, beta and Y molecular sieves are all from commercial purchase.
PREPARATION EXAMPLE 1-1
Taking 60 g of mesoporous MWW-22 molecular sieve powder, then compounding 40 g of alumina with the powder, kneading, forming into strips, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 5 hours. The molded sample was exchanged with an ammonium chloride solution at 80℃for 8 hours, washed with deionized water, dried at 150℃for 5 hours, and calcined at 500℃for 6 hours. Thus obtaining the required solid acid catalyst G1.
PREPARATION EXAMPLES 1-2
60 g of mesoporous beta molecular sieve powder is taken, 40 g of alumina is taken to be compounded with the powder, kneaded, formed into a strip shape, dried for 12 hours at 120 ℃, and then baked for 5 hours at 400 ℃. The molded sample was exchanged with an ammonium chloride solution at 80℃for 8 hours, washed with deionized water, dried at 150℃for 5 hours, and calcined at 500℃for 6 hours. Thus obtaining the required solid acid catalyst G2.
Preparation examples 1 to 3
60 g of mesoporous Y molecular sieve powder is taken, 40 g of alumina is taken to be compounded with the powder, kneaded, formed into a strip shape, dried for 12 hours at 120 ℃, and then baked for 5 hours at 400 ℃. The molded sample was exchanged with an ammonium chloride solution at 80℃for 8 hours, washed with deionized water, dried at 150℃for 5 hours, and calcined at 500℃for 6 hours. Thus obtaining the required solid acid catalyst G3.
Preparation examples 1 to 4
Taking 30 g of mesoporous MWW-22 molecular sieve powder and 30 g of mesoporous beta molecular sieve powder, then taking 40 g of alumina to be compounded with the powder, kneading the powder, forming the mixture into strips, drying the strips at 120 ℃ for 12 hours, and then roasting the strips at 400 ℃ for 5 hours. The molded sample was exchanged with an ammonium chloride solution at 80℃for 8 hours, washed with deionized water, dried at 150℃for 5 hours, and calcined at 500℃for 6 hours. Thus obtaining the required solid acid catalyst G4.
Preparation examples 1 to 5
60 g of phosphotungstic acid powder is taken, 40 g of alumina is taken to be compounded with the powder, the mixture is kneaded and formed into a strip shape, the strip shape is dried for 12 hours at 120 ℃, and then the strip shape is baked for 5 hours at 400 ℃. Thus obtaining the required solid acid catalyst G5.
Preparation examples 1 to 6
70 g of phosphotungstic acid powder is taken, 30 g of alumina is taken to be compounded with the powder, the mixture is kneaded and formed into a strip shape, the strip shape is dried for 12 hours at 120 ℃, and then the strip shape is baked for 5 hours at 400 ℃. Thus obtaining the required solid acid catalyst G6.
Preparation examples 1 to 7
35 g of phosphotungstic acid powder and 35 g of phosphomolybdic acid powder are taken, 30 g of alumina is taken to be compounded together with the phosphomolybdic acid powder, the mixture is kneaded and molded into a strip shape, the strip shape is dried for 12 hours at 120 ℃, and then the strip shape is baked for 5 hours at 400 ℃. Thus obtaining the required solid acid catalyst G7.
The following preparation examples are presented to illustrate the preparation of dehydrogenation catalysts
PREPARATION EXAMPLE 2-1
100 g of alumina carrier is taken, 3 g of Pt is loaded, the carrier is dried for 12 hours at 120 ℃, and the carrier is roasted for 5 hours at 550 ℃. The obtained sample is reduced for 6 hours at 450 ℃ and the hydrogen volume space velocity is 300 hours -1 . The desired dehydrogenation catalyst H1 is obtained.
PREPARATION EXAMPLE 2-2
100 g of alumina carrier is taken, 5 g of Pt is loaded, the carrier is dried for 12 hours at 120 ℃, and the carrier is roasted for 5 hours at 550 ℃. The obtained sample is reduced for 6 hours at 450 ℃ and the hydrogen volume space velocity is 300 hours -1 . Thus obtaining the required dehydrogenation catalyst H2.
PREPARATION EXAMPLES 2-3
100 g of alumina carrier is taken, 10 g of Ni is loaded, the alumina carrier is dried for 12 hours at 120 ℃, and the alumina carrier is roasted for 5 hours at 550 ℃. The obtained sample is reduced for 6 hours at 480 ℃ and the hydrogen volume space velocity is 300 hours -1 . Thus obtaining the required dehydrogenation catalyst H3.
PREPARATION EXAMPLES 2 to 4
100 g of alumina carrier is taken, 15 g of Ni is loaded, the alumina carrier is dried for 12 hours at 120 ℃, and the alumina carrier is roasted for 5 hours at 550 ℃. The obtained sample was reduced at 500℃for 6 hours and the hydrogen volume space velocity was 300 hours -1 . Thus obtaining the required dehydrogenation catalyst H4.
Example 1
(1) 10G of the solid acid catalyst G1 was taken and cyclohexylbenzene and cyclohexene were subjected to alkylation reaction in a fixed bed reactor. The mass space velocity of cyclohexene was 0.5h -1 The molar ratio of cyclohexylbenzene to cyclohexene was 4. The reaction temperature was 160℃and the reaction pressure was 2.0MPa and the reaction time was 1000 hours, and the reaction mixture was collected and the alkylation reaction results were shown in Table 1.
(2) 100 g of the mixture obtained in the step (1) was taken and placed in a reduced pressure distillation apparatus, the system pressure was reduced to 3kPa, the temperature of the column bottom was increased to 245℃and the C6 and C12 components in the remaining mixture were distilled off, and the composition of the column bottom components obtained by distillation was shown in Table 2.
(3) Dehydrogenation reaction of dehydrogenation catalyst H1 and dicyclohexylbenzene obtained in tower kettle in step (2) is carried out on a fixed bed reactor, and the catalyst loading amount is 10 g, the reaction conditions are: the mass space velocity of dicyclohexylbenzene is 1.0h -1 The reaction temperature is 350 ℃, the molar ratio of hydrogen to dicyclohexylbenzene is 1.5, the reaction pressure is 1.0MPa, the reaction time is 1000 hours, the reaction mixture is collected to be hydrogenated terphenyl type high-temperature heat conduction oil S1, and the dehydrogenation reaction result is shown in Table 3.
The product index of the resulting high temperature heat transfer oil is shown in table 4, according to the corresponding requirements for L-QD340 in national standard specification GB 23971.
Examples 2 to 7
The procedure of example 1 was followed except that the solid catalysts were G2-G7, respectively.
The alkylation reaction results are shown in Table 1, and the composition of the distilled bottoms is shown in Table 2.
Example 8
The procedure of example 1 was followed except that the hydrogenation catalyst was H2, the resulting high temperature heat transfer oil was S8, and the composition of the hydrogenation reaction product was as shown in Table 3.
Example 9
The procedure of example 1 was followed except that the hydrogenation catalyst was H3, the resulting high temperature heat transfer oil was S9, and the composition of the hydrogenation reaction product was as shown in Table 3.
Example 10
The procedure of example 1 was followed except that the hydrogenation catalyst was H4, the resulting high temperature heat transfer oil was S10, and the composition of the hydrogenation reaction product was as shown in Table 3.
Example 11
The procedure of example 1 was followed except that the alkylation reaction conditions in step (1) were such that the mass space velocity of cyclohexene was 0.8h -1 The molar ratio of cyclohexylbenzene to cyclohexene was 5. The reaction temperature was 210℃and the reaction pressure was 2.5MPa, the reaction time was 1000 hours, and the reaction mixture was collected, and the alkylation reaction results were shown in Table 1. .
Example 12
The procedure of example 1 was followed except that the reduced pressure distillation conditions in step (2) were such that the system pressure was reduced to 8kPa and the column bottoms temperature was increased to 275 ℃.
Example 13
The procedure of example 1 was followed except that the dehydrogenation reaction conditions in step (3) were such that the mass space velocity of dicyclohexylbenzene was 1.0h -1 The reaction temperature was 345 ℃, the molar ratio of hydrogen to dicyclohexylbenzene was 1.0, the reaction pressure was 0.8MPa, and the reaction time was 1000 hours.
TABLE 1 Cyclohexylbenzene and cyclohexene alkylation reaction results (wt.%)
| Numbering device | Cyclohexene conversion | Dicyclohexylbenzene selectivity |
| Example 1 | 96.3 | 96.2 |
| Example 2 | 92.3 | 95.2 |
| Example 3 | 87.0 | 93.7 |
| Example 4 | 80.3 | 92.2 |
| Example 5 | 88.3 | 85.5 |
| Example 6 | 90.2 | 91.2 |
| Example 7 | 85.3 | 87.8 |
| Example 11 | 94.3 | 90.0 |
TABLE 2 composition of tower bottoms (wt.%)
TABLE 3 dehydrogenation reaction results of dicyclohexylbenzene (wt.%)
TABLE 4 various detection indexes of the products obtained by the invention
As can be seen from the results in Table 4, the hydrogenated terphenyl high-temperature heat conduction oil has lower pour point, low requirement on natural environment temperature and wide application range, and in addition, the product has good thermal stability, low deterioration rate and long expected service life, and the deterioration rate is only 3.8% after being heated for 1000h at 340 ℃.
The hydrogenated terphenyl high-temperature heat conduction oil has low energy consumption in the preparation process, high yield of hydrogenated terphenyl and good application prospect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A hydrogenated terphenyl type high temperature heat transfer oil comprising: dicyclohexylbenzene, cyclohexylbiphenyl and terphenyl, and the content of cyclohexylbiphenyl in the heat transfer oil is not less than 40 wt%.
2. The heat transfer oil according to claim 1, wherein the total amount of dicyclohexylbenzene, cyclohexylbiphenyl and terphenyl is not less than 70 wt%, preferably not less than 80 wt%;
preferably, the content of cyclohexylbiphenyl is not less than 45% by weight, preferably 45 to 55% by weight.
3. The heat transfer oil according to claim 1, wherein the dicyclohexylbenzene content is 5 to 60 wt%, the cyclohexylbiphenyl content is 40 to 80 wt%, and the terphenyl content is 1 to 30 wt%;
preferably, the dicyclohexylbenzene content is 10-40 wt%, the cyclohexylbiphenyl content is 45-55 wt%, and the terphenyl content is 5-20 wt%.
4. The heat transfer oil of any of claims 1-3, wherein the dicyclohexylbenzene is from an alkylation reaction of cyclohexylbenzene with cyclohexene and/or cyclohexanol;
and/or, the cyclohexylbiphenyl and terphenyl are derived from the dehydrogenation of dicyclohexylbenzene.
5. The preparation method of the hydrogenated terphenyl type high-temperature heat conduction oil comprises the following steps of:
(1) Carrying out alkylation reaction on cyclohexylbenzene and cyclohexene and/or cyclohexanol under the action of a solid acid catalyst to generate a mixture containing dicyclohexylbenzene;
(2) Removing the C6-C12 component from the dicyclohexylbenzene-containing mixture to obtain dicyclohexylbenzene;
(3) And (3) partially dehydrogenating dicyclohexylbenzene under the action of a dehydrogenation catalyst to obtain hydrogenated terphenyl type high-temperature heat conduction oil.
6. The preparation method according to claim 5, wherein the solid acid catalyst comprises a mesoporous molecular sieve and/or a heteropolyacid and a binder;
preferably, the mesoporous molecular sieve is selected from at least one of a mesoporous MWW-22 molecular sieve, a mesoporous Y-type molecular sieve and a mesoporous beta molecular sieve, and preferably the mesoporous MWW-22 molecular sieve and/or the mesoporous Y-type molecular sieve;
preferably, the heteropolyacid is selected from phosphomolybdic acid and/or phosphotungstic acid, preferably phosphotungstic acid;
preferably, the binder is selected from at least one of alumina, silica, clay and diatomaceous earth, and further preferably alumina;
preferably, the content of mesoporous molecular sieve and/or heteropolyacid is 50-70 wt% and the content of binder is 30-50 wt%, based on the total amount of the solid acid catalyst.
7. The production method according to claim 5 or 6, wherein the alkylation reaction conditions include: the reaction temperature is 150-230 ℃, the reaction pressure is 1.5-3.5MPa, and the molar ratio of the cyclohexylbenzene to cyclohexene and/or cyclohexanol is 1-6:1, cyclohexene and/or cyclohexanol mass space velocity of 0.1-2.0h -1 。
8. The process according to claim 5, wherein in the step (2), the C6-C12 component in the dicyclohexylbenzene-containing mixture is removed by distillation under reduced pressure;
preferably, the conditions of the reduced pressure distillation include: the temperature is 220-300 ℃ and the vacuum degree is 2-10kPa.
9. The production method according to claim 5, wherein the dehydrogenation catalyst comprises a carrier and a dehydrogenation metal;
preferably, the support is selected from alumina and/or silica;
preferably, the dehydrogenation metal is selected from at least one of group VIII non-noble metals and/or at least one of noble metals, further preferably at least one of Ni, pt and Pd;
preferably, the carrier is present in an amount of 85 to 99 wt% and the dehydrogenation metal is present in an amount of 1 to 15 wt% based on the total amount of dehydrogenation catalyst.
10. The production method according to claim 5 or 9, wherein the conditions of partial dehydrogenation include: the reaction temperature is 300-450 ℃, the molar ratio of hydrogen to dicyclohexylbenzene is 0.1-30, and the mass airspeed of dicyclohexylbenzene is 0.1-2.0h -1 The reaction pressure is 0.5-1.5MPa;
preferably, the conditions of partial dehydrogenation include: the reaction temperature is 320-400 ℃, the molar ratio of hydrogen to dicyclohexylbenzene is 0.5-20, and the mass airspeed of dicyclohexylbenzene is 0.8-1.5h -1 The reaction pressure is 0.6-1.0MPa.
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