CN111662148B - Method and device for continuously preparing bridge-type tetrahydrodicyclopentadiene - Google Patents
Method and device for continuously preparing bridge-type tetrahydrodicyclopentadiene Download PDFInfo
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- CN111662148B CN111662148B CN201910171980.4A CN201910171980A CN111662148B CN 111662148 B CN111662148 B CN 111662148B CN 201910171980 A CN201910171980 A CN 201910171980A CN 111662148 B CN111662148 B CN 111662148B
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- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
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- 239000010935 stainless steel Substances 0.000 description 8
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000852 hydrogen donor Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method and a device for preparing bridge-type tetrahydrodicyclopentadiene through continuous hydrogenation of dicyclopentadiene, wherein the method comprises the following steps: adding dicyclopentadiene and hydrogen-supplying reagent into a fixed bed reactor, and continuously converting dicyclopentadiene into bridge-type tetrahydrodicyclopentadiene in the presence of hydrogenation catalyst, wherein the reaction temperature is 100-240 ℃, the reaction pressure is 0.1-2.0 MPa, and the volume space velocity is 0.2-10h ‑1 . The method can continuously prepare bridge tetrahydrodicyclopentadiene, has low requirements on equipment and equipment, simple process, mild reaction conditions, high yield of reaction products and good stability of the catalyst, and has industrial application prospect.
Description
Technical Field
The invention relates to a method and a device for continuously preparing bridge-type tetrahydrodicyclopentadiene, in particular to a method and a device for continuously preparing bridge-type tetrahydrodicyclopentadiene by hydroconverting dicyclopentadiene.
Background
Dicyclopentadiene (DCPD) is mainly derived from C5 fraction which is a byproduct in the ethylene preparation process by petroleum pyrolysis and light benzene fraction which is a byproduct in coal coking, is a dimer of cyclopentadiene, is an important chemical intermediate, and is widely used for synthesizing unsaturated polyester polymers, preparing high-density aviation fuel and medical materialsAnd (3) preparing materials and the like. The completely hydrogenated product of the bridge tetrahydrodicyclopentadiene (Endo-THDCPD) is a solid high-density fuel with excellent performance, and can be further isomerized into the pendent tetrahydrodicyclopentadiene (Exo-THDCPD) and adamantane. Exo-THDCPD is also known as JP-10, can be used singly or in a compound way, is used in the field of aviation fuel, and adamantane can be used as high-density jet fuel, is an important fine chemical raw material, and is widely used in the fields of medicine, materials and the like. The research on the hydroconversion of DCPD at home and abroad is mature, but all the research and conversion are carried out by H 2 As a hydrogen source, the reaction pressure is higher, and for the research of continuous conversion, higher hydrogen-oil volume ratio is often needed, hydrogen is not recycled, the hydrogenation process is more intense, the temperature is easy to fly, and the service life of the catalyst is shorter and is not easy to meet the industrial continuous production requirement. The current hydrogen source is mainly the conversion of traditional fossil energy, and the price is relatively high, so that the waste of the hydrogen not only increases the raw material cost, but also causes lower atom utilization rate. In addition, high pressure is used, so that high requirements on equipment, operation, investment, safety and the like are brought.
CN 1911878A discloses a method for preparing tetrahydrodicyclopentadiene from dicyclopentadiene through continuous hydrogenation, wherein in the process, reaction raw materials and hydrogen are mixed by a venturi ejector, and the molar ratio of dicyclopentadiene to hydrogen is 1: (2-5), the reaction pressure is 0.9MPa-1.5MPa, the reaction heat is required to be removed, the yield of the tetrahydrodicyclopentadiene is 90%, the hydrogen utilization rate in the process is low, the requirements on equipment and equipment are high, and the operation safety is high. In the hydrogenation step of dicyclopentadiene disclosed in CN 107417485A, higher hydrogen pressure of 1MPa-4MPa is also required, the volume ratio of hydrogen to oil is 200-400, and the hydrogen has higher requirements on safety, equipment and operation and low hydrogen utilization rate.
Disclosure of Invention
The invention provides a method for preparing bridge-type tetrahydrodicyclopentadiene by continuously hydroconverting dicyclopentadiene, which aims at the problems of low hydrogen utilization rate, high operating pressure, strong reaction heat release and the like in the continuous hydroconversion process of dicyclopentadiene.
The invention also provides a device for preparing bridge-type tetrahydrodicyclopentadiene by continuously hydroconverting dicyclopentadiene.
The invention provides a continuous method for preparing bridge tetrahydrodicyclopentadiene, which comprises the following steps: adding dicyclopentadiene and a hydrogen supply reagent into a fixed bed reactor, and continuously converting the dicyclopentadiene into bridge-type tetrahydrodicyclopentadiene in the presence of a hydrogenation catalyst, wherein the reaction temperature is 100-240 ℃, the reaction pressure is 0.1-2 MPa, and the volume space velocity is 0.5-10h -1 。
The hydrogen-supplying reagent is one or more selected from C1-C3 fatty alcohol and fatty acid.
The invention provides a device for continuously preparing bridge tetrahydrodicyclopentadiene, which comprises: the device comprises a raw material premixing tank, a fixed bed reactor and a condensation separation tank, a pipeline for conveying hydrogen supply reagent to the raw material premixing tank, a pipeline for conveying dicyclopentadiene to the raw material premixing tank, a pipeline for conveying reaction solvent to the raw material premixing tank, a pipeline for conveying premixed raw materials from the raw material premixing tank to the fixed bed reactor, a pipeline for conveying reacted materials from the fixed bed reactor to the condensation separation tank, a pipeline for outputting products in the condensation separation tank, and a pipeline for conveying supernatant liquid in the condensation separation tank to the raw material premixing tank.
The method of the invention uses hydrogen-supplying reagent to replace the traditional H 2 The method for preparing Endo-THDCPD by continuously hydrogenating DCPD through a fixed bed reactor simplifies the equipment flow, greatly reduces the equipment requirement, does not need to operate under the state of hydrogen with pressure, has milder reaction and does not generate the traditional H 2 The catalyst has better activity and stability due to the deactivation problem of the catalyst caused by the easy occurrence of the flying temperature of hydrogenation.
The method has high utilization rate of raw materials, recycling of unreacted raw materials, continuous preparation of bridge tetrahydrodicyclopentadiene, high conversion rate of the dicyclopentadiene and yield of the bridge tetrahydrodicyclopentadiene, and by-product of bridge dihydro dicyclopentadiene. Therefore, the method for preparing the bridge-type tetrahydrodicyclopentadiene is safer, more green and more flexible.
Drawings
FIG. 1 is a schematic diagram of a preferred embodiment of the reaction apparatus of the present invention. The method comprises the following steps: a raw material premixing tank 1, a raw material preheating tank 2, a fixed bed reactor 3 and a condensation separation tank 4, a line 5 for transporting a hydrogen-supplying agent to the raw material premixing tank 1, a line 6 for transporting dicyclopentadiene to the raw material premixing tank 1, a line 7 for transporting a reaction solvent to the raw material premixing tank 1, a line 8 for transporting a premixed raw material from the raw material premixing tank 1 to the raw material preheating tank 2, a line 9 for transporting a preheated raw material from the raw material preheating tank 2 to the fixed bed reactor 3, a line 10 for transporting a reacted material from the fixed bed reactor 3 to the condensation separation tank 4, a line 11 for outputting a product in the condensation separation tank 4, and a line 12 for transporting an supernatant in the condensation separation tank 4 to the raw material premixing tank 1.
Detailed Description
The invention provides a continuous method for preparing bridge tetrahydrodicyclopentadiene, which comprises the following steps: adding dicyclopentadiene and hydrogen-supplying reagent into a fixed bed reactor, and continuously converting dicyclopentadiene into bridge-type tetrahydrodicyclopentadiene in the presence of hydrogenation catalyst, wherein the reaction temperature is 100-240 ℃, the reaction pressure is 0.1-2 MPa, and the volume space velocity is 0.2-10h -1 。
According to the invention, dicyclopentadiene and a hydrogen supply reagent are preferably premixed uniformly in a raw material tank, and then pumped into a raw material preheating tank for preheating, preferably to 40-80 ℃, and then enter a fixed bed reactor for reaction. The raw material preheating can also be carried out in a fixed bed reactor or a raw material premixing tank.
According to the invention, the product bridge tetrahydrodicyclopentadiene can be separated from the reaction solvent and the hydrogen-supplying reagent by the cooling part at the product collecting position, and the reaction solvent and the hydrogen-supplying reagent can be recycled to the raw material tank.
The dicyclopentadiene preferably forms a solution with an organic solvent which is a moderately polar oxygen-containing solvent such as C1-C3 aliphatic alcohols, furans, and the like, preferably methanol, ethanol, isopropanol, tetrahydrofuran, and the like. Wherein the mass fraction of dicyclopentadiene in the solution (simply referred to as substrate concentration) is 10% -80%, preferably 20% -50%.
According to the invention, the hydrogen donor agent is selected from one or more of C1-C3 fatty alcohols or fatty acids, such as methanol, ethanol, formic acid, acetic acid, preferably formic acid and methanol. Wherein the hydrogen-supplying agent is added in an amount such that when the hydrogen-supplying agent is completely converted, the hydrogen-supplying agent is theoretically supplied in an amount at least ensuring complete saturation of dicyclopentadiene, for example, the amount may be 1 to 8 times the theoretical amount, and preferably 3 to 4 times the theoretical amount.
When the hydrogen donor reagent and the organic solvent are selected to be the same (e.g., methanol or ethanol), the hydrogen donor reagent and the organic solvent are added according to the respective addition amounts and addition modes, and the addition amounts and the addition modes are not mutually influenced.
According to the method of the invention, the hydrogenation catalyst can be a supported metal catalyst, and the metal can be a noble metal or a non-noble metal, for example, one or more metals selected from Pd, pt, ru, rh, ir, ni, cu and the like, preferably Pd, pt and the like. The carrier may be a conventional carrier, for example, one selected from activated carbon, al 2 O 3 、SiO 2 The carrier such as Y molecular sieve is preferably activated carbon and Al 2 O 3 . The active metal loading may be from 1wt% to 20wt%, preferably from 5wt% to 15wt%, based on the support mass.
According to the process of the present invention, the reaction pressure may be either normal pressure or 0.1MPa to 2MPa, preferably 0.1MPa to 1MPa, more preferably 0.1MPa to 0.8MPa. The reaction temperature is from 100℃to 240℃and preferably from 120℃to 220℃and more preferably from 150℃to 200 ℃. The volume airspeed is 0.2 to 10h -1 Preferably 0.5 to 6 hours -1 More preferably 1 to 3 hours -1 。
The invention provides a device for continuously preparing bridge tetrahydrodicyclopentadiene, which comprises: the device comprises a raw material premixing tank, a fixed bed reactor and a condensation separation tank, a pipeline for conveying hydrogen supply reagent to the raw material premixing tank, a pipeline for conveying dicyclopentadiene to the raw material premixing tank, a pipeline for conveying reaction solvent to the raw material premixing tank, a pipeline for conveying premixed raw materials from the raw material premixing tank to the fixed bed reactor, a pipeline for conveying reacted materials from the fixed bed reactor to the condensation separation tank, a pipeline for outputting products in the condensation separation tank, and a pipeline for conveying supernatant liquid in the condensation separation tank to the raw material premixing tank.
In the device, a raw material preheating tank can be arranged behind the raw material premixing tank, and the preheated raw material enters the fixed bed reactor again.
In the device of the invention, the raw material premixing tank and the raw material preheating tank can be replaced by a reaction tank with stirring and heating functions.
In the device, each pipeline is provided with a valve and a sampling port, so that the technical index of the conveyed materials can be monitored; except the pipeline 10, the other pipelines are all provided with conveying pumps which can control the material transmission; the delivery pump, the valve and the like are automatically controlled by a central control room.
Specific embodiments of the present invention are further described below with reference to examples.
Example 1 (influence of different reaction temperatures)
Taking an isopropanol solution of 40wt% of dicyclopentadiene as a raw material; at 10% Pd/Al 2 O 3 Is a hydrogenation catalyst; formic acid is taken as a hydrogen supply reagent, and the addition amount is 3 times of the theoretical amount required by complete saturation of DCPD; then preheated to 50 ℃ and fed into a fixed bed reactor, the influence of different reaction temperatures on DCPD conversion and Endo-THDCPD selectivity is examined.
Reaction conditions: preparing the dicyclopentadiene and the isopropanol into a dicyclopentadiene solution with 40 weight percent, adding the dicyclopentadiene solution into a raw material tank, adding a corresponding amount of hydrogen supply reagent into the raw material tank, and stirring for 10 minutes at normal temperature. Then placing the catalyst in the middle of a stainless steel reaction tube, gradually heating the fixed bed to 100-200 ℃ at 10 ℃/min, and then using a plunger pump for 2.0h -1 Is added to the reactor. The system pressure was maintained at 0.5MPa by adjusting the back pressure valve. After the system is stabilized for 10 hours, sampling is carried out at an outlet for gas chromatography analysis, and the influence of different reaction temperatures is examined, wherein the reaction results are as follows:
example 2 (influence of different feed space velocities)
Taking an isopropanol solution of 40wt% of dicyclopentadiene as a raw material; at 10% Pd/Al 2 O 3 Is a hydrogenation catalyst; formic acid is taken as a hydrogen supply reagent, and the addition amount is 3 times of the theoretical amount required by complete saturation of DCPD; then preheated to 50 ℃, and introduced into a fixed bed reactor, the influence of different reaction airspeeds on DCPD conversion and Endo-THDCPD selectivity is examined.
Reaction conditions: preparing the dicyclopentadiene and the isopropanol into a dicyclopentadiene solution with 40 weight percent, adding the dicyclopentadiene solution into a raw material tank, adding a corresponding amount of hydrogen supply reagent into the raw material tank, and stirring for 10 minutes at normal temperature. Then the catalyst is placed in the middle of a stainless steel reaction tube, the fixed bed is gradually heated to 160 ℃ at 10 ℃/min, and then the feeding is performed by a plunger pump. The back pressure valve is regulated to keep the pressure of the system at 0.5MPa, after the system is stabilized for 10 hours, sampling is carried out at an outlet for gas chromatographic analysis, the influence of different feeding airspeeds is examined, and the reaction results are as follows:
example 3 (influence of different Hydrogen-donating Agents addition amounts)
Taking an isopropanol solution of 40wt% of dicyclopentadiene as a raw material; at 10% Pd/Al 2 O 3 Is a hydrogenation catalyst; taking formic acid as a hydrogen supply reagent, wherein the addition amount is 1-4 times of the theoretical amount required by complete saturation of DCPD; then preheated to 50 ℃, and fed into a fixed bed reactor to examine the influence of the addition amount of the hydrogen-supplying agent on the DCPD conversion rate and the Endo-THDCPD selectivity.
Reaction conditions: dicyclopentadiene and isopropanol solvent are prepared into a dicyclopentadiene solution with 40 weight percent, the dicyclopentadiene solution is added into a raw material tank, and then hydrogen-supplying reagents with different amounts are added into the raw material tank, and the mixture is stirred for 10 minutes at normal temperature. Then the catalyst is placed in the middle of a stainless steel reaction tube, the fixed bed is gradually heated to 160 ℃ at 10 ℃/min, and then a plunger pump is utilizedAt 2.0h -1 Is fed at a feed space velocity. The back pressure valve is regulated to keep the pressure of the system to be 0.5MPa, after the system is stabilized for 10 hours, the gas chromatographic analysis is carried out by sampling at the outlet, the influence of the addition amounts of different hydrogen supplying reagents is examined, and the reaction results are as follows:
example 4 (influence of different types of Hydrogen donating agents)
Taking an isopropanol solution of 40wt% of dicyclopentadiene as a raw material; at 10% Pd/Al 2 O 3 Is a hydrogenation catalyst; formic acid, methanol, ethanol or acetic acid is taken as a hydrogen supply reagent, and the addition amount is 3 times of the theoretical amount required by complete saturation of DCPD; the effect of different hydrogen donor reagent types on DCPD conversion and Endo-THDCPD selectivity was then examined directly at room temperature in a fixed bed reactor.
Reaction conditions: dicyclopentadiene and isopropanol solvent are prepared into a dicyclopentadiene solution with 40 weight percent, the dicyclopentadiene solution is added into a raw material tank, and then corresponding amounts of different types of hydrogen supply reagents are added into the raw material tank, and the mixture is stirred for 10 minutes at normal temperature. Then the catalyst is placed in the middle of a stainless steel reaction tube, the fixed bed is gradually heated to 160 ℃ at 10 ℃/min, and then a plunger pump is utilized for 2.0h -1 Is fed at a feed space velocity. The back pressure valve is regulated to keep the pressure of the system to be 0.5MPa, after the system is stabilized for 10 hours, the gas chromatographic analysis is carried out by sampling at an outlet, the influence of different hydrogen supply reagent types is examined, and the reaction result is as follows:
example 5 (influence of different reaction solvents)
Taking 40wt% dicyclopentadiene solution as a raw material; at 10% Pd/Al 2 O 3 Is a hydrogenation catalyst; formic acid is taken as a hydrogen supply reagent, and the addition amount is 3 times of the theoretical amount required by complete saturation of DCPD; then preheating to 50 ℃, introducing the mixture into a fixed bed reactor, and inspecting the reaction solventEffect on DCPD conversion and Endo-THDCPD selectivity.
Reaction conditions: dicyclopentadiene and different solvents are prepared into a dicyclopentadiene solution with 40 weight percent, the dicyclopentadiene solution is added into a raw material tank, and then a corresponding amount of hydrogen supply reagent is added into the raw material tank, and the mixture is stirred for 10 minutes at normal temperature. Then the catalyst is placed in the middle of a stainless steel reaction tube, the fixed bed is gradually heated to 160 ℃ at 10 ℃/min, and then a plunger pump is utilized for 2.0h -1 Is fed at a feed space velocity. And (3) keeping the system pressure at normal pressure, after the system is stabilized for 10 hours, sampling at an outlet for gas chromatographic analysis, and observing the influence of different reaction solvents, wherein the reaction results are as follows:
example 6 (influence of different substrate concentrations)
Taking isopropanol solutions of dicyclopentadiene with different substrate concentrations as raw materials; at 10% Pd/Al 2 O 3 Under the hydrogenation catalyst, formic acid is used as a hydrogen supply reagent, and the addition amount is 3 times of the theoretical amount required by complete saturation of DCPD; then preheated to 50 ℃ and fed into a fixed bed reactor, the effect of different substrate concentrations on DCPD conversion and Endo-THDCPD selectivity was examined.
Reaction conditions: dicyclopentadiene and isopropanol solvent are prepared into dicyclopentadiene solutions with different concentrations, the dicyclopentadiene solutions are added into a raw material tank, and then a corresponding amount of hydrogen supply reagent is added into the raw material tank, and the mixture is stirred for 10min at normal temperature. Then placing hydrogenation catalyst in the middle of stainless steel reaction tube, heating the fixed bed to 160 deg.C at 10 deg.C/min gradually, and using plunger pump for 2.0 hr -1 Is fed at a feed space velocity. The back pressure valve is regulated to keep the pressure of the system to be 0.5MPa, after the system is stabilized for 10 hours, sampling is carried out at an outlet for gas chromatographic analysis, the influence of different substrate concentrations is examined, and the reaction result is as follows:
example 7 (influence of different catalysts)
Taking an isopropanol solution of 40wt% of dicyclopentadiene as a raw material; under different hydrogenation catalysts, formic acid is used as a hydrogen supply reagent, and the addition amount is 3 times of the theoretical amount required by complete saturation of DCPD; the reaction mixture was then preheated to 50℃and passed into a fixed bed reactor, and the effect of the different catalysts on DCPD conversion and Endo-THDCPD selectivity was examined.
Reaction conditions: dicyclopentadiene and isopropanol solvent are prepared into a dicyclopentadiene solution with 40 weight percent, the dicyclopentadiene solution is added into a raw material tank, and then a corresponding amount of hydrogen-supplying reagent is added into the raw material tank, and the mixture is stirred for 10 minutes at normal temperature. Then placing different types of hydrogenation catalysts in the middle of a stainless steel reaction tube, gradually heating a fixed bed to 160 ℃ at 10 ℃/min, and then using a plunger pump for 2.0h -1 Is fed at a feed space velocity. The back pressure valve is regulated to keep the pressure of the system to be 0.5MPa, after the system is stabilized for 10 hours, sampling is carried out at an outlet for gas chromatographic analysis, the influence of different hydrogenation catalysts is examined, and the reaction results are as follows:
example 8 (investigation of catalyst stability)
Taking an isopropanol solution of 40wt% of dicyclopentadiene as a raw material; at 10% Pd/Al 2 O 3 Is a hydrogenation catalyst; formic acid is taken as a hydrogen supply reagent, and the addition amount is 4 times of the theoretical amount required by complete saturation of DCPD; then preheated to 50 ℃, and introduced into a fixed bed reactor to examine the DCPD conversion and the variation of Endo-THDCPD selectivity with the reaction time.
Reaction conditions: dicyclopentadiene and isopropanol solvent are prepared into a dicyclopentadiene solution with 40 weight percent, the dicyclopentadiene solution is added into a raw material tank, and then a corresponding amount of hydrogen-supplying reagent is added into the raw material tank, and the mixture is stirred for 10 minutes at normal temperature. The catalyst is then placed in the middle of a stainless steel reaction tube, and the fixed bed is fixedGradually heating to 160 ℃ at 10 ℃/min, and then using a plunger pump for 2.0h -1 Is fed at a feed space velocity. The back pressure valve is regulated to keep the pressure of the system to be 0.5MPa, gas chromatographic analysis is carried out on samples at the outlet every 10 hours, the change of the DCPD conversion rate and the Endo-THDCPD selectivity along with the reaction time is examined, and the reaction result is as follows:
Claims (2)
1. a method for preparing bridge tetrahydrodicyclopentadiene through continuous hydrogenation, which comprises the following steps: adding dicyclopentadiene and a hydrogen supply reagent into a fixed bed reactor, and continuously converting the dicyclopentadiene into bridge-type tetrahydrodicyclopentadiene in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst is a supported metal catalyst, the metal is selected from Pd and Pt, and the carrier is Al 2 O 3 The active metal loading is 10wt percent to 15wt percent; the hydrogen supply reagent is formic acid; the dicyclopentadiene forms a solution with an organic solvent selected from the group consisting of isopropanol and tetrahydrofuran; the reaction temperature is 160-200 ℃, the reaction pressure is 0.5-0.8 MPa, and the volume airspeed is 1-3h -1 The addition amount of the hydrogen supply reagent is 3-4 times of the theoretical demand amount.
2. The method according to claim 1, wherein the dicyclopentadiene forms a solution with the organic solvent, and the mass fraction of the dicyclopentadiene in the solution is 10% to 50%.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4270014A (en) * | 1979-04-30 | 1981-05-26 | Ashland Oil, Inc. | Production of high energy fuel |
CN101215218A (en) * | 2008-01-16 | 2008-07-09 | 西安近代化学研究所 | Method for preparing exo-tetrahydrocyclopentadiene |
CN108117474A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of method that furfuryl alcohol prepares JP-10 aviation fuel |
-
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- 2019-03-07 CN CN201910171980.4A patent/CN111662148B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4270014A (en) * | 1979-04-30 | 1981-05-26 | Ashland Oil, Inc. | Production of high energy fuel |
CN101215218A (en) * | 2008-01-16 | 2008-07-09 | 西安近代化学研究所 | Method for preparing exo-tetrahydrocyclopentadiene |
CN108117474A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of method that furfuryl alcohol prepares JP-10 aviation fuel |
Non-Patent Citations (3)
Title |
---|
光照下非贵金属催化的1-辛烯转移加氢反应;贾颖萍等;《化学通报》;20091231(第11期);第1029-1032页 * |
双环戊二烯连续加氢用镍基催化剂研究;安高军等;《化学推进剂与高分子材料》;20161231(第03期);第34-38页 * |
安高军等.双环戊二烯连续加氢用镍基催化剂研究.《化学推进剂与高分子材料》.2016,(第03期),第34-38页. * |
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