CN113264806B - Method for preparing tetrahydronaphthalene, cis-decalin and trans-decalin by naphthalene hydrogenation - Google Patents
Method for preparing tetrahydronaphthalene, cis-decalin and trans-decalin by naphthalene hydrogenation Download PDFInfo
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Abstract
The invention relates to a method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation, which comprises the following steps: heating and liquefying raw material refined naphthalene, mixing with inlet hydrogen, carrying out primary and secondary hydrogenation reactions under the action of a hydrogenation catalyst, carrying out multistage heat exchange on the reacted high-temperature material, and then carrying out cold high-fraction and cold low-fraction separation to obtain a hydrogenation product; the hydrogenated product enters the rectification separation of subsequent products. Compared with the prior art, the invention has the following advantages and beneficial effects: the solid naphthalene raw material crusher is arranged, so that the naphthalene liquefaction process is accelerated. The device adopts the solid naphthalene liquefaction process, so that the hydrogenation process is convenient to control. The hydrogenation part adopts a cold flow splitting process, thereby simplifying the process. The industrial naphthalene is used as the raw material, so that the production cost is reduced, and the raw material adaptability is strong. The single raw material and the catalyst can simultaneously produce various products, thereby realizing the diversification of the products.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and relates to a method for preparing tetrahydronaphthalene, cis-decalin and trans-decalin by naphthalene hydrogenation.
Background
Decahydronaphthalene is an important derivative of naphthalene, has cis-trans 2 configurations, is a colorless and transparent liquid at normal temperature, has extremely strong dissolving capacity, and can be used as a solvent for engineering plastics, such as nylon 6, nylon 10, ultrahigh molecular weight polyethylene fibers and synthetic high molecular weight aliphatic polyester, as well as a solvent and a paint remover for paint, grease, resin, rubber and the like.
In addition, decahydronaphthalene has been successfully applied to high-end chemical projects as a gas phase heat transfer oil. The decalin can be synthesized by catalytic hydrogenation of naphthalene, the generated decalin can be subjected to catalytic hydrogenolysis under proper conditions to release pure hydrogen, and the research of using the decalin as a novel hydrogen storage material by utilizing the reaction of catalytic hydrogenation of naphthalene and catalytic hydrogenolysis of decalin is also more. With the rise of hydrogen fuel cells, reliable hydrogen storage materials are required to be guaranteed, and decalin becomes an excellent hydrogen storage material which is more and more valued in the industry and is successfully applied to the hydrogen fuel cells, so that the decalin market is more and more extensive in the future.
Trans-and cis-decalins have their respective uses: the thermal stability of the trans-decalin is superior to that of long-chain alkane, so that the trans-decalin is an additive component which is necessary to improve the thermal stability of aviation kerosene, and meanwhile, the trans-decalin crystal is also a TFT type LED liquid crystal display material with novel structure and excellent performance; the cis-decalin is mainly used for producing capric acid, and further producing engineering plastics nylon 6, nylon 10, a plasticizer and the like.
In recent years, the industrial technologies for synthesizing high-value-added products such as tetrahydronaphthalene or decalin by hydrogenation by taking naphthalene as a raw material are more abroad, the research is mainly performed at home, and especially, decahydronaphthalene production manufacturers are basically absent at home (2 manufacturers at home are all intermittent processes, the yield is less than 200 tons/year, and the quality cannot be compared with that of imported products at all), the method almost completely depends on import, and the price is high.
With the gradual application of decahydronaphthalene in new fields such as engineering plastic solvents, dry-process production of ultra-high molecular weight polyethylene fibers, high-grade fuels, hydrogen storage raw materials and the like, the development and application of naphthalene fine processing technology, the breakthrough of foreign technical barriers and the breaking of the current situation of import dependence have important economic and practical significance in the face of wide market demands. Meanwhile, with the continuous widening and demand increasing of the application field of naphthalene derivatives, the problems of source resource surplus, seeking of comprehensive utilization of resources and development and utilization of industrial naphthalene to produce products with high added values are key problems to be solved urgently at present, and the method has important significance and demonstration effects on adjusting industrial structures, realizing transformation and upgrading and realizing green sustainable development of chemical enterprises.
Tetralin (also called tetralin, tetralin), is an alicyclic aromatic hydrocarbon. It is a colorless liquid with a naphthalene odor. Is an important derivative product of naphthalene. Tetrahydronaphthalene is insoluble in water and miscible with all customary solvents. The solvent is an ideal high-boiling point solvent, can be widely applied to the industrial fields of paint, coating, printing ink (used as a solvent of paint, coating and printing ink), hard alloy (used as a hard alloy forming agent), medicine, paper making and the like, and has been used by various domestic industries for a long time.
Tetralin soluble grease, oxidized linseed oil, rubber, wax, asphalt, phenolic resin, naphthalene and iodine. It can be used for paint and floor and shoe polishing agent.
Because the tetrahydronaphthalene can dissolve almost all organic matters, the upper and lower paint coatings have good viscosity. The tetralin has the functions of improving leveling and gloss in a paint system, improving the adhesion between paint layers and serving as an oxygen donor in the drying process of the oil. The tetrahydronaphthalene can dissolve rosin, pectin, alkyd resin, coumarone resin and modified formaldehyde resin. Therefore, tetrahydronaphthalenes can be used to make high-grade paints, which give the paints good flow, high gloss and smooth surfaces. Can be used for manufacturing printing ink, plastic ink and automobile paint.
Since tetralin has a high boiling point and is evaporated only in a small amount even at a temperature of 180 ℃, it can be used as a high boiling point solvent. The tetralin can also be used as degreasing agent, softening agent, and absorbent of low boiling point organic compound vapor. The tetrahydronaphthalene can be automatically oxidized and can be used as a drying agent.
Tetrahydronaphthalenes are used as insect repellents and as turpentine substitutes. The tetralin is oxidized by liquid phase air to produce tetralin ketone or tetralin alcohol, and the tetralin ketone is dehydrogenated to produce methyl naphthol, which is an intermediate for preparing carbaryl as insecticide.
Tetrahydronaphthalenes are used to make lubricants and to reduce the viscosity of high viscosity oils. Can be used for producing heat conducting oil in dimethyl furan.
Electrophilic tetralin substitution occurs mainly at the 6-position, such as nitration, sulfonation, bromination, acetylation. Oxidizing with potassium permanganate to obtain phthalic acid. Dehydrogenating with sulfur, selenium, etc. to obtain naphthalene. Used as a solvent and a raw material for producing medicines and the like. Mixing with alcohol and benzene can be used as a component of fuel for internal combustion engines.
Tetralin is also used in industrial fields such as manganese detection, chromatographic analysis reagents, hard alloy (used as a hard alloy forming agent), medicine, paper making and the like.
At present, the tetrahydronaphthalene product in China has large demand and is in short supply. The production of tetrahydronaphthalene depends on market demand, the capacity of upstream naphthalene and production scale, the intermediate position of the tetrahydronaphthalene in the processing process is very important, and although the tetrahydronaphthalene is increased by more than 10% in recent years, the annual capacity cannot meet the market demand due to the performance limit of the catalyst and the requirement of process conditions.
The method for preparing decahydronaphthalene by naphthalene hydrogenation has been studied for as early as seventy-eight years, for example: J.Soc.chem.Ing.,1927,46.454 and Rec.trav.chim.,1934,53.821 report the reaction mechanism, process parameters, the action of various catalysts and the like for preparing decahydronaphthalene by naphthalene hydrogenation.
Japanese patent JP160515A, published by Xiongwen and Pingzhoulang on 6/3/2003, reports "a method for producing decalin by a two-step hydrogenation reaction of naphthalene". The method comprises the following steps: the first step of naphthalene hydrogenation generates tetrahydronaphthalene, and after the rectification and separation of the product, the second step of hydrogenation generates decahydronaphthalene from the tetrahydronaphthalene.
In the patent application with the application number of 200310106565.X, tetrahydronaphthalene is adopted as a solvent of solid raw material naphthalene, a nickel catalyst is used, decahydronaphthalene is synthesized in one step in a reaction kettle at a relatively low temperature and pressure, the reaction pressure is 6-12MPa, the reaction temperature is 180-220 ℃, the Liquid Hourly Space Velocity (LHSV) is 0.5-1, the conversion rate of naphthalene is more than 98 percent, the yield of decahydronaphthalene is 98 percent, and the yield of byproducts is less than 1 percent. However, the reaction pressure is high, the energy consumption is high, and the equipment investment is large. Although this method gives good results, the production efficiency is very low because of the batch operation in the reaction vessel, and it is difficult to meet the large-scale market demand.
In the patent application with application number 200510041404.6, a continuous hydrogenation synthesis method of decahydronaphthalene is disclosed, which is a production method for continuously hydrogenating naphthalene to synthesize decahydronaphthalene in a steady trickle bed catalytic reactor under certain pressure and temperature conditions. Decahydronaphthalene or tetrahydronaphthalene is used as a solvent of solid raw material naphthalene, a catalyst such as platinum aluminum or nickel aluminum is used, and decahydronaphthalene is continuously hydrogenated and synthesized under the conditions of 2-15 MPa, 120-280 ℃, liquid hourly volume space velocity (LHSV) of 0.1-5.0 h < -1 >, and hydrogen-oil ratio of 1-3000 NL/L. The conversion rate of naphthalene is 70-99%, and the side reactant is less than 1%. Although the technology can realize continuous production, the technology has poor stability in control and higher operation cost, and the conversion rate of naphthalene is to be further improved.
As naphthalene hydrogenation is a series reaction, in the presence of a hydrogenation catalyst, a first benzene ring is firstly saturated, then a second benzene ring is saturated under a harsher condition, and complete hydrogenation is carried out to generate decahydronaphthalene. However, in the prior art, alumina is used as a catalyst carrier, and transition metals such as nickel, molybdenum, tungsten, cobalt and the like are used as active components, or noble metals such as Pt and Pd are used as active components, so that the following problems exist:
(1) the noble metal is used as an active metal component, the cost is high, and particularly in recent years, the price of the noble metal is increased, so that the cost of the catalyst is high, and the application and popularization of the catalyst are limited; moreover, since the noble metal is very sensitive to impurities, even a small amount of impurities, such as compounds of sulfur, nitrogen, etc., can easily cause poisoning of the noble metal catalyst, shorten the service life and cause increase of the use cost;
(2) most of the currently used refined catalyst carriers are alumina and contain some elements such as silicon, titanium and the like, so that the catalyst has different degrees of acidity, side reactions such as cracking of aromatic hydrocarbon and the like are often caused in the hydrogenation process, and the selectivity of a target product is low;
(3) because the existing catalyst has low hydrogenation performance, the conversion rate of naphthalene is low in the naphthalene hydrogenation process, if the temperature is increased, side reactions such as cracking and the like occur, and the selectivity of a target product is low;
(4) because the pore channels of the alumina carrier are secondary pores with larger pore diameters, the alumina carrier has no restriction capacity on reactants or products, so that various products can be generated, and the selectivity of target products is lower;
(5) some catalysts incorporate more acidic molecular sieves, such as BETA or Y type molecular sieves, which result in increased side reactions, resulting in not only decreased tetrahydronaphthalene selectivity but also significant loss of the more expensive naphthalene.
From the above, it is known that research on a method for preparing tetrahydronaphthalene, cis-decalin and trans-decalin by naphthalene hydrogenation is an important research subject.
Disclosure of Invention
The purpose of the invention is: in order to solve one of the problems, the method for preparing the tetrahydronaphthalene, the cis-decahydronaphthalene and the trans-decahydronaphthalene by naphthalene hydrogenation is provided, and the diversity, the industrialization and the continuous production of cis-decahydronaphthalene, trans-decahydronaphthalene and tetrahydronaphthalene products are realized by adopting a two-stage hydrogenation and rectification separation method.
In order to achieve the purpose, the invention provides a method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation, which is characterized by comprising the following steps: the method comprises the following steps:
s1: heating and liquefying raw material refined naphthalene, mixing with inlet hydrogen, carrying out primary and secondary hydrogenation reactions under the action of a hydrogenation catalyst, carrying out multistage heat exchange on the reacted high-temperature material, and then carrying out cold high-fraction and cold low-fraction separation to obtain a hydrogenation product; s2: the hydrogenation product enters the rectification separation of the subsequent products.
Preferably, in step S1, the solid naphthalene raw material crushed by the crusher is injected into the naphthalene melting kettle 2 through the naphthalene feeding bin 1, the solid naphthalene is heated and liquefied, then pumped out by the feeding pump 3 to be mixed with inlet hydrogen, and enters the front hydrogenation reactor 4 to perform a primary hydrogenation reaction, a primary hydrogenation reaction product is mixed with the inlet hydrogen, and enters the rear hydrogenation reactor 5 to perform a secondary hydrogenation reaction, and the secondary hydrogenation reaction product is subjected to multi-stage heat exchange by the heat exchanger 6, and then sequentially passes through the high-molecular tank 7 and the low-molecular tank 8, and is separated to obtain a hydrogenation product, wherein the hydrogenation product is a mixed product of tetrahydronaphthalene, cis-decalin and trans-decalin in different proportions; step S2, mixing products of tetrahydronaphthalene, cis-decalin and trans-decalin in different proportions, entering a light component removal tower 11, removing light oil and storing the light oil in a storage tank, entering a heavy component removal tower 12 from a liquid phase at the bottom of the light component removal tower 11, entering a light phase tower 13 from a separation product at the top of the heavy component removal tower 12, entering a heavy phase tower 14 from a separation product at the bottom of the heavy component removal tower 12, separating trans-decalin at the top of the light phase tower 13 and storing the trans-decalin in the storage tank, separating cis-decalin at the bottom of the light phase tower 13 and storing the cis-decalin in the storage tank, and separating tetrahydronaphthalene at the top of the heavy phase tower 14 and storing the tetrahydronaphthalene in the storage tank.
Preferably, in step S1, the front hydrogenation reactor 4 has a material inlet, a pipeline connected to the material inlet has a hydrogen injection port, the hydrogen inlet of the front hydrogenation reactor 4 is communicated with the outlet of the fresh hydrogen compressor 9, and fresh hydrogen is injected through the fresh hydrogen compressor 9, the rear hydrogenation reactor 5 has a material inlet, a pipeline connected to the material inlet has a hydrogen injection port, and the hydrogen injection port is communicated with the outlet of the recycle hydrogen compressor 10 and is injected with recycle hydrogen through the recycle hydrogen compressor 10.
Preferably, in step S1, the secondary hydrogenation reaction product after heat exchange enters the high separation tank 7, the refined cold high separation gas and the refined cold high separation oil are separated, the refined cold high separation gas is sent to the recycle hydrogen compressor 10 to be pressurized as recycle hydrogen, the refined cold high separation oil enters the low separation tank 8, and the hydrogenation product is separated from the low separation tank 8.
Preferably, the high-pressure separator 7 adopts a high-pressure separator for gas-liquid two-phase separation, and the low-pressure separator 8 adopts a low-pressure separator for oil-gas-water three-phase separation.
The invention carries out primary and secondary hydrogenation reactions under the action of a naphthalene hydrogenation catalyst, and the naphthalene hydrogenation catalyst comprises five components of NTP-A, NTP-B, NTH-A, NTH-B and NTH-C.
Preferably, the front hydrogenation reactor 4 and the rear hydrogenation reactor 5 adopt a multi-section cold shock type fixed bed, and the temperature of the reaction bed layer is controlled.
Preferably, the side wall of the multi-section cold shock type fixed bed is provided with a side wall hydrogenation port, and cold hydrogen is used for controlling the temperature of the catalyst inlet of the hydrogenation reactor, so that the operation flexibility of the reactor is improved, and the service life of the catalyst is prolonged.
Preferably, the bottom product of the heavy phase column 14 is refluxed to the melting tank 2.
Preferably, a washing water injection point is provided on the upstream side of the reaction effluent air cooler to prevent ammonium bisulfide salts from being precipitated at a low temperature portion and from clogging the air cooler by deposition.
Preferably, the light-phase removal tower, the heavy-phase removal tower, the light-phase tower and the heavy-phase tower are all provided with a reboiler, so that the rectifying tower is provided with a rectifying section and a stripping section, clear division of light-phase and heavy-phase components is realized, and the quality of products is ensured.
The working principle of the invention is as follows:
the hydrogenation reaction process of raw material naphthalene: the method comprises the following steps of crushing and heating liquefaction of a solid naphthalene raw material, pressure boosting of a liquid naphthalene raw material, compression of circulating hydrogen and new hydrogen, heat exchange of the raw material and a product, primary hydrogenation reaction, secondary hydrogenation, gas phase cooling of a reaction product, gas-liquid phase high-pressure separation and gas-liquid phase low-pressure separation in sequence to obtain mixed products of tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene in different proportions, and the process also comprises a desulfurization process of circulating hydrogen in the high-pressure separation process of a facility.
② the separation process of tetrahydronaphthalene and decahydronaphthalene of the hydrogenation reaction product: removing light oil from the hydrogenation product through a light-phase tower system, separating decalin and tetralin through a heavy-phase tower system, separating the decalin with cis-form and trans-form structures through a light-phase tower system, and separating a high-purity tetralin product through a heavy-phase tower system; if the cis-structure and trans-structure decalin does not need to be separated, the de-heavy tower system can directly extract the cis-structure and trans-structure mixed decalin product so as to realize the diversity of the product.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the solid naphthalene raw material crusher is arranged, so that the naphthalene liquefaction process is accelerated.
2. The device adopts a solid naphthalene liquefaction process, so that the control of a hydrogenation process is facilitated.
3. The hydrogenation part adopts a cold flow splitting process, thereby simplifying the process.
4. The product fractionation part is provided with a four-tower flow path, so that the operation flexibility of the device is improved.
5. The cold hydrogen is used for controlling the temperature of the catalyst inlet of the hydrogenation reactor, so that the operation flexibility of the reactor is improved, and the service life of the catalyst is prolonged.
6. The mixed hydrogen heat exchange heating scheme before mixing the naphthalene raw material with hydrogen is adopted, so that the precipitation of solid naphthalene caused by the reduction of the mixing temperature of cold hydrogen mixed into the liquid naphthalene raw material is avoided.
7. Adopts the scheme of gas-liquid two-phase separation of a high-pressure separator and oil-gas-water three-phase separation of a low-pressure separator.
8. And a washing water injection point is arranged on the upstream side of the reaction effluent air cooler to prevent ammonium bisulfide salt from being precipitated at a low-temperature part and blocking the air cooler by deposition.
9. The four rectifying towers are provided with the reboilers, so that the rectifying towers are provided with a rectifying section and a stripping section, clear division of light-phase and heavy-phase components is realized, and the quality of products is ensured.
10. The industrial naphthalene is used as the raw material, so that the production cost is reduced, and the raw material adaptability is strong.
11. The single raw material and the catalyst can simultaneously produce various products, thereby realizing the diversification of the products.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a schematic flow diagram of the steps of naphthalene hydrogenation to produce tetrahydronaphthalene and cis-trans decahydronaphthalene according to the present invention;
FIG. 2 is a schematic flow chart of the separation step of tetrahydronaphthalene, cis-decalin and trans-decalin.
In the figure: 1. The system comprises a naphthalene feeding bin 2, a naphthalene melting kettle inner 3, a feeding pump 4, a front hydrogenation reactor 5, a rear hydrogenation reactor 6, a heat exchanger 7, a high molecular tank 8, a low molecular tank 9, a fresh hydrogen compressor 10, a circulating hydrogen compressor 11, a light phase removal tower 12, a heavy phase removal tower 13, a light phase tower 14 and a heavy phase tower.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
example 1, a process for the hydrogenation of naphthalene to produce tetrahydronaphthalene, cis-decalin, and trans-decalin.
The process flow diagram is shown in figure 1 and figure 2: injecting a solid naphthalene raw material crushed by a crusher into a naphthalene melting kettle 2 through a naphthalene feeding bin 1, heating and liquefying the solid naphthalene, pumping out the liquefied solid naphthalene through a feeding pump 3, mixing the liquefied solid naphthalene with inlet hydrogen, entering a front hydrogenation reactor 4 for primary hydrogenation reaction, mixing a primary hydrogenation reaction product with the inlet hydrogen, entering a rear hydrogenation reactor 5 for secondary hydrogenation reaction, performing multi-stage heat exchange on the secondary hydrogenation reaction product through a heat exchanger 6, sequentially passing through a high-molecular tank 7 and a low-molecular tank 8, and separating to obtain a hydrogenation product, wherein the hydrogenation product is a mixed product of tetrahydronaphthalene, cis-decalin and trans-decalin in different proportions; mixed products of tetrahydronaphthalene, cis-decalin and trans-decalin in different proportions enter a light component removal tower 11, light oil is removed and stored in a storage tank, a liquid phase at the bottom of the light component removal tower 11 enters a heavy component removal tower 12, a separation product at the top of the heavy component removal tower 12 enters a light phase tower 13, a separation product at the bottom of the heavy component removal tower 12 enters a heavy phase tower 14, trans-decalin is separated from the top of the light phase tower 13 and stored in the storage tank, cis-decalin is separated from the bottom of the light phase tower 13 and stored in the storage tank, and tetrahydronaphthalene is separated from the top of the heavy phase tower 14 and stored in the storage tank.
In step S1, the front hydrogenation reactor 4 has a material inlet, a pipeline connected to the material inlet has a hydrogen injection port, the hydrogen inlet of the front hydrogenation reactor 4 is communicated with the outlet of the fresh hydrogen compressor 9, fresh hydrogen is injected through the fresh hydrogen compressor 9, the rear hydrogenation reactor 5 has a material inlet, a pipeline connected to the material inlet has a hydrogen injection port, the hydrogen injection port is communicated with the outlet of the recycle hydrogen compressor 10, and recycle hydrogen is injected through the recycle hydrogen compressor 10.
In step S1, the secondary hydrogenation product after heat exchange enters the high separation tank 7, the refined cold high-pressure gas and the refined cold high-pressure oil are separated, the refined cold high-pressure gas is sent to the recycle hydrogen compressor 10 and is pressurized to 18.3MPa to be used as recycle hydrogen, the refined cold high-pressure oil enters the low separation tank 8, and the hydrogenation product is separated from the low separation tank 8.
The high-pressure separator 7 adopts a high-pressure separator to separate gas from liquid, and the low-pressure separator 8 adopts a low-pressure separator to separate oil, gas and water.
The invention carries out primary and secondary hydrogenation reactions under the action of a naphthalene hydrogenation catalyst, and the naphthalene hydrogenation catalyst comprises five components of NTP-A, NTP-B, NTH-A, NTH-B and NTH-C.
The front hydrogenation reactor 4 and the rear hydrogenation reactor 5 adopt a multi-section cold shock type fixed bed to control the temperature of a reaction bed layer.
The side wall of the multi-section cold shock type fixed bed is provided with a side wall hydrogenation port, and cold hydrogen is used for controlling the temperature of the catalyst inlet of the hydrogenation reactor, so that the operation flexibility of the reactor is improved, and the service cycle of the catalyst is prolonged.
The bottom product of the heavy phase tower 14 flows back to the melting kettle 2.
And a washing water injection point is arranged on the upstream side of the reaction effluent air cooler to prevent ammonium bisulfide salt from being precipitated at a low-temperature part and depositing to block the air cooler.
The light-phase removal tower, the heavy-phase removal tower, the light-phase tower and the heavy-phase tower are all provided with reboilers, so that the rectifying tower is provided with a rectifying section and a stripping section, clear division of light-phase and heavy-phase components is realized, and the quality of products is ensured.
Wherein, the reactor is fed with 100 percent liquid naphthalene, the reaction temperature is 250 ℃, the reaction pressure is 9.0MPa, the catalyst volume space velocity (H-1) is 5.3, the hydrogen-oil ratio (V/V) is 1200, the conversion per pass of naphthalene is 98.2 percent, the selectivity of tetrahydronaphthalene is more than 98 percent, the selectivity of cis-decahydronaphthalene is 0.8 percent, the selectivity of trans-decahydronaphthalene is 1.2 percent, the yield of tetrahydronaphthalene measured by a gas chromatograph is more than 99.4 percent.
Example 2:
the difference from the first embodiment is that the reactor is fed with 100 percent of liquid naphthalene, the reaction temperature is 320 ℃, the reaction pressure is 9.0MPa, the volume space velocity (H-1) of the catalyst is 5.3, the hydrogen-oil ratio (V/V) is 1200, the conversion per pass of naphthalene is 99.2 percent, the selectivity of tetrahydronaphthalene is 98.7 percent, the selectivity of cis-decahydronaphthalene is 0.5 percent, the selectivity of trans-decahydronaphthalene is 0.8 percent, the yield of tetrahydronaphthalene measured by a gas chromatograph is over 99.4 percent.
Example 3:
the difference from the first embodiment is that the reactor is fed with 100% liquid naphthalene, the reaction temperature is 250 ℃, the reaction pressure is 9.3MPa, the catalyst volume space velocity (H-1) is 5.3, the hydrogen-oil ratio (V/V) is 1800, the conversion per pass of naphthalene is 98.7%, the selectivity of cis-decalin is 46.7%, the selectivity of trans-decalin is 49.6%, the selectivity of tetrahydronaphthalene is 3%, the yield of cis-decalin and trans-decalin can reach more than 99.2% when measured by a gas chromatograph, and the yield of tetrahydronaphthalene can reach more than 98.7% when measured by a gas chromatograph.
Example 4:
the difference from the first embodiment lies in that the reactor is fed with 100% liquid naphthalene, the reaction temperature is 320 ℃, the reaction pressure is 9.3MPa, the catalyst volume space velocity (H-1) is 5.3, the hydrogen-oil ratio (V/V) is 1800, the single-pass conversion rate of naphthalene is 99.5%, the selectivity of cis-decalin is 26.5%, the selectivity of trans-decalin is 70.6%, and the selectivity of tetrahydronaphthalene is 2.7%, the yield of cis-decalin and trans-decalin can reach more than 99.2% when the liquid naphthalene is separated by a rectification system, and the yield of tetrahydronaphthalene can reach more than 98.2% when the liquid naphthalene is measured by a gas chromatograph.
Example 5:
the difference from the first embodiment is that the reactor is fed with 100 percent of liquid naphthalene, the reaction temperature is 320 ℃, the reaction pressure is 9.3MPa, the volume space velocity (H-1) of the catalyst is 5.3, the hydrogen-oil ratio (V/V) is 1200, the conversion per pass of naphthalene is 99.6 percent, the selectivity of tetrahydronaphthalene is 99.2 percent, the selectivity of cis-decahydronaphthalene is 0.3 percent, the selectivity of trans-decahydronaphthalene is 0.4 percent, the yield of tetrahydronaphthalene is over 99.4 percent as measured by a gas chromatograph.
Example 6:
the difference from the first embodiment lies in that the reactor is fed with 100% liquid naphthalene, the reaction temperature is 320 ℃, the reaction pressure is 9.0MPa, the catalyst volume space velocity (H-1) is 5.3, the hydrogen-oil ratio (V/V) is 1800, the single-pass conversion rate of naphthalene is 99.4%, the selectivity of cis-decalin is 22.5%, the selectivity of trans-decalin is 68.4%, the selectivity of tetrahydronaphthalene is 8.3%, the yield of cis-decalin and trans-decalin can reach more than 98.6% when the liquid naphthalene is separated by a rectification system, and the yield of tetrahydronaphthalene can reach more than 98.7% when the liquid naphthalene is measured by a gas chromatograph.
In summary, the above method is used to control the saturation degree of the reaction by adjusting the hydrogen-oil ratio under the catalytic action of the catalyst, the naphthalene raw material is first partially saturated to generate tetrahydronaphthalene, the tetrahydronaphthalene is further fully saturated to generate decahydronaphthalene product, the decahydronaphthalene is subjected to cis-trans isomerization reaction under different pressures and temperatures, and the temperature and pressure of the reaction are adjusted based on the cis-trans isomerization reaction, and the cis-decahydronaphthalene and trans-decahydronaphthalene in the mixed product are different in proportion (i.e. different in isomerization degree) under different temperatures and pressures. Then according to the difference of boiling points among all components in the mixed product, the separation among different components is realized through a rectifying tower so as to obtain high-purity tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene products.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A method for preparing tetrahydronaphthalene, cis-decalin and trans-decalin by naphthalene hydrogenation is characterized by comprising the following steps:
step S1, injecting the solid naphthalene raw material crushed by the crusher into a naphthalene melting kettle (2) through a naphthalene feeding bin (1), heating and liquefying the solid naphthalene, pumping out the liquefied solid naphthalene through a feeding pump (3), mixing the liquefied solid naphthalene with inlet hydrogen, feeding the liquefied solid naphthalene into a front hydrogenation reactor (4) for primary hydrogenation reaction, mixing a primary hydrogenation reaction product with the inlet hydrogen, feeding the primary hydrogenation reaction product into a rear hydrogenation reactor (5) for secondary hydrogenation reaction, performing multi-stage heat exchange on the secondary hydrogenation reaction product through a heat exchanger (6), sequentially passing through a high molecular tank (7) and a low molecular tank (8), and separating to obtain a hydrogenation product, wherein the hydrogenation product is a mixed product of tetrahydronaphthalene, cis-decalin and trans-decalin in different proportions;
and S2, mixing products of tetrahydronaphthalene, cis-decalin and trans-decalin in different proportions, entering a light component removal tower (11), removing light oil and storing the light component removal tower in a storage tank, entering a liquid phase at the bottom of the light component removal tower (11) into a heavy component removal tower (12), entering a separation product at the top of the heavy component removal tower (12) into a light phase tower (13), entering a separation product at the bottom of the heavy component removal tower (12) into a heavy phase tower (14), separating trans-decalin at the top of the light phase tower (13) and storing the trans-decalin in the storage tank, separating cis-decalin at the bottom of the light phase tower (13) and storing the cis-decalin in the storage tank, and separating tetrahydronaphthalene at the top of the heavy phase tower (14) and storing the cis-decalin the storage tank.
2. The method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation according to claim 1, which is characterized in that: in the step S1, the front hydrogenation reactor (4) is provided with a material inlet, a pipeline connected with the material inlet is provided with a hydrogen injection port, the hydrogen inlet of the front hydrogenation reactor (4) is communicated with the outlet of a new hydrogen compressor (9), new hydrogen is injected through the new hydrogen compressor (9), the rear hydrogenation reactor (5) is provided with a material inlet, a pipeline connected with the material inlet is provided with a hydrogen injection port, the hydrogen injection port is communicated with the outlet of a circulating hydrogen compressor (10), and circulating hydrogen is injected through the circulating hydrogen compressor (10).
3. The method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation according to claim 2, which is characterized in that: in step S1, the secondary hydrogenation reaction product after heat exchange enters a high separation tank (7), refined cold high separation gas and refined cold high separation oil are separated, the refined cold high separation gas is sent to a recycle hydrogen compressor (10) to be pressurized as recycle hydrogen, the refined cold high separation oil enters a low separation tank (8), and the hydrogenation product is separated from the low separation tank (8).
4. The method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation according to claim 3, wherein: the high-pressure separator (7) adopts a high-pressure separator to separate gas and liquid, and the low-pressure separator (8) adopts a low-pressure separator to separate oil, gas and water.
5. The method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation according to claim 4, wherein: the front hydrogenation reactor and the rear hydrogenation reactor both adopt a multi-section cold shock type fixed bed.
6. The method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation according to claim 5, wherein the method comprises the following steps: the side wall of the multi-section cold shock type fixed bed is provided with a side wall hydrogenation port, and the inlet temperature of the catalyst of the hydrogenation reactor is controlled by cold hydrogen.
7. The method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation according to claim 1, which is characterized in that: the method is characterized in that 100% of liquid naphthalene is fed into a reactor, the reaction temperature is 250 ℃, the reaction pressure is 9.0MPa, the catalyst volume space velocity (H-1) is 5.3, the hydrogen-oil ratio (V/V) is 1200, the conversion per pass of naphthalene is 98.2%, the tetrahydronaphthalene selectivity is over 98%, the cis-decahydronaphthalene selectivity is 0.8%, the trans-decahydronaphthalene is 1.2%, and the yield of the tetrahydronaphthalene measured by a gas chromatograph is over 99.4%.
8. The method for preparing tetrahydronaphthalene, cis-decahydronaphthalene and trans-decahydronaphthalene by naphthalene hydrogenation according to claim 1, which is characterized in that: the method is characterized in that 100% of liquid naphthalene is fed into a reactor, the reaction temperature is 320 ℃, the reaction pressure is 9.0MPa, the catalyst volume space velocity (H-1) is 5.3, the hydrogen-oil ratio (V/V) is 1200, the conversion per pass of naphthalene is 99.2%, the tetrahydronaphthalene selectivity is 98.7%, the cis-decahydronaphthalene selectivity is 0.5%, the trans-decahydronaphthalene is 0.8%, and the yield of the tetrahydronaphthalene can reach more than 99.4% by a gas chromatograph through separation of a rectification system.
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| CN1732142A (en) * | 2002-12-03 | 2006-02-08 | 默克专利股份有限公司 | Method for production naphthalene derivatives |
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| CN106565398A (en) * | 2016-11-08 | 2017-04-19 | 西南化工研究设计院有限公司 | Method for producing decalin through crude naphthalene hydrodesulfurization |
| CN107814677A (en) * | 2016-09-14 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of process units and method of decahydronaphthalenes isomers |
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| CN1732142A (en) * | 2002-12-03 | 2006-02-08 | 默克专利股份有限公司 | Method for production naphthalene derivatives |
| WO2006083409A2 (en) * | 2004-12-22 | 2006-08-10 | Exxonmobil Chemical Patents, Inc. | Production of liquid hydorocarbons from methane |
| CN104193578A (en) * | 2014-08-21 | 2014-12-10 | 邯郸惠达化工有限公司 | Method for producing decahydronaphthalene and tetrahydronaphthalene by naphthalene hydrogenation |
| CN107814677A (en) * | 2016-09-14 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of process units and method of decahydronaphthalenes isomers |
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