CN105541542A - Technique for continuously producing decahydronaphthalene from industrial naphthalene - Google Patents
Technique for continuously producing decahydronaphthalene from industrial naphthalene Download PDFInfo
- Publication number
- CN105541542A CN105541542A CN201610080521.1A CN201610080521A CN105541542A CN 105541542 A CN105541542 A CN 105541542A CN 201610080521 A CN201610080521 A CN 201610080521A CN 105541542 A CN105541542 A CN 105541542A
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- CN
- China
- Prior art keywords
- reaction
- liquid
- hydrogenation
- gas
- perhydronaphthalene
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/47—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing ten carbon atoms
- C07C13/48—Completely or partially hydrogenated naphthalenes
- C07C13/50—Decahydronaphthalenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- 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
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
Abstract
The invention relates to a method for continuously producing decahydronaphthalene from industrial naphthalene, belonging to the technical field of chemical industry. The method comprises the following steps: mixing industrial naphthalene and a solvent, mixing with hydrogen gas, heating to the reaction temperature, sending into a primary hydrogenation reactor to perform hydrogenation reaction, separating the hydrogenation products by a gas-liquid separator, removing impurities from the gas-phase product by a gas washing tower to obtain hydrogen gas for recycling, and refluxing part of the liquid-phase product into a raw material mixing tank as a solvent; and sending the rest liquid-phase product into a secondary hydrogenation reactor to perform hydrogenation reaction, passing the reaction products through the gas-liquid separator, recycling the hydrogen gas, sending the liquid phase into a product rectification tower, and rectifying to remove a small amount of light components, thereby obtaining the high-purity decahydronaphthalene. The technique provided by the invention has the characteristics of high adaptability, high naphthene conversion rate, fewer side reactions and high decahydronaphthalene purity.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of production method of perhydronaphthalene, particularly relating to a kind of take NAPTHALENE FLAKES. (INDUSTRIAL GRADE） as the hydrogenation technique of raw material production perhydronaphthalene.
Background technology
Perhydronaphthalene, as condensed ring hydrocarbon polymer, all has very extensive and important application in chemical industry, electronic industry and pharmaceutical industries, and it can be used as the solvent of coating, for extracting fat and wax, replaces turps to be used for the manufacture etc. of shoe polish, floor wax.Perhydronaphthalene main application is as excellent high boiling organic solvent, dissolves some macromolecular compound, in textile industry, has important application.
Foreign study hydrogenated naphthalene synthesizes perhydronaphthalene and is mostly proceed step by step in autoclave, and naphthalene is changed into naphthane by the first step typical catalyst high-pressure hydrogenation, and second step precious metal is made catalyzer and carry out degree of depth hydrogenation under comparatively mild conditions.
The report of current China synthesis perhydronaphthalene achievement in research is less.CN200310106565 discloses a kind of synthetic method of perhydronaphthalene, take naphthalene as raw material, naphthane is solvent, in batch still, react the technique of one-step synthesis perhydronaphthalene, naphthalene transformation efficiency reaches 98%, perhydronaphthalene productive rate 98%, side reaction thing is less than 1%, although the method obtains good effect, owing to being batch operation, production efficiency is low.Xiamen University patent CN101602644A adopts interrupter method, in autoclave, naphthalene is hydrogenated to perhydronaphthalene, and its used catalyst is Ni/ γ-Al
2o
3, solvent is hexanaphthene, and reaction conditions is: temperature 80-200 DEG C, pressure 2-5MPa, liquid hourly space velocity 9-13h
-1, naphthalene transformation efficiency is 100%, and perhydronaphthalene yield is 99%.CN200510041404.6 discloses a kind of continuous hydrogenation synthesis method of perhydronaphthalene, the method stable state trickle bed catalyticreactor, under certain pressure and temperature condition naphthalene continuous hydrogenation synthesis perhydronaphthalene production method, the transformation efficiency of naphthalene is 70% ~ 99%, and side reaction product is less than 1%.Although the method achieves continuous seepage, the transformation efficiency of naphthalene needs to be improved further.Report in Japanese Patent JP160515A " method that naphthalene two step hydrogenation reaction manufactures perhydronaphthalene ".Its method is: naphthalene the first step hydrogenation generates naphthane, and after being separated by product rectification, second step generates perhydronaphthalene by naphthane hydrogenation.Barbul, the people such as MariusAurel describe a kind of tarry cut generation naphthane of hydrogenated naphthalene content 90%, the method for perhydronaphthalene in patent " methodandapparatusforpurificationofnaphthalencefromcokin g ", reaction conditions is: temperature 350-510 DEG C, pressure 3-6MPa, hydrogen/solvent ratio is 300-2500Nm
3/ m
3, solution feed rate is 1-10m
3/ h, catalyzer is containing 12-16% molybdenum oxide and 3-5.5% cobalt oxide and (or) nickel oxide, and carrier is porous alumina.
In above patent report, mostly adopt with the refined naphthalene of the foreign matter content such as low-sulfur, nitrogen for raw material, produce perhydronaphthalene through a step or two step hydrogenation.Be that raw material adopts two step hydrogenation to produce many employings non-precious metal catalyst of perhydronaphthalenes with thick naphthalene, be difficult to production high purity perhydronaphthalene, more cannot use NAPTHALENE FLAKES. (INDUSTRIAL GRADE） continuous seepage high purity perhydronaphthalene.
Summary of the invention
The required technical problem solved of the present invention solves the problem poor to adaptability to raw material in prior art, product purity is low, there is provided a kind of processing method of NAPTHALENE FLAKES. (INDUSTRIAL GRADE） continuous seepage perhydronaphthalene, the method is that raw material adopts two sections of tandem process to produce the hydrogenation method of perhydronaphthalene with NAPTHALENE FLAKES. (INDUSTRIAL GRADE）.
A kind of NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of the present invention is the processing method of raw material continuous seepage perhydronaphthalene, and with NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (thick naphthalene) for raw material, by two-stage hydrogenation series connection production high purity perhydronaphthalene, this processing method comprises:
1) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and solvent with the volume ratio of 1:1 ~ 10 after raw material mixing tank mixes, mixing with hydrogen and entering one-stage hydrogenation reactor hydrogenation reaction after being heated to temperature of reaction, hydrogenation products is after gas-liquid separator separates, gas-phase product through scrubber tower removing impurities matter obtain hydrogen recycle use, liquid product a part as solvent refluxing to raw material mixing tank; Wherein said one-stage hydrogenation reaction conditions is: reaction pressure 1 ~ 5MPa, temperature of reaction, and hydrogen liquid volume ratio 100 ~ 1000:1, liquid hourly space velocity counts 0.1 ~ 5h with NAPTHALENE FLAKES. (INDUSTRIAL GRADE）
-1, catalyzer is the non-precious metal catalyst of desulfurization, denitrogenation and hydrogenating function, in simple substance, and metalloid content 10wt% ~ 50wt%, described one-stage hydrogenation reactor is isothermal shell and tube reactor;
2) another part liquid product enters the further hydrogenation reaction of second-stage hydrogenation reactor, and reaction product is after gas-liquid separator, and hydrogen recycle uses, and liquid phase enters product rectifying tower, removes after a small amount of light constituent obtain high purity perhydronaphthalene through rectifying; Wherein said secondary hydrogenation reaction conditions is: reaction pressure 5 ~ 20MPa, temperature of reaction 200 ~ 400 DEG C, hydrogen liquid volume ratio 100 ~ 1000:1, liquid hourly space velocity 0.1 ~ 5h
-1, catalyzer adopts the noble metal catalyst of high hydrogenation activity, and in simple substance, bullion content is content 0.05wt% ~ 5wt%, and described second stage reactor is heat-insulating fixed-bed reactor.
The method that the present invention produces perhydronaphthalene compared with prior art tool has the following advantages:
1) take NAPTHALENE FLAKES. (INDUSTRIAL GRADE） as raw material, reduce the production cost of perhydronaphthalene, adaptability to raw material is strong;
2) non-precious metal catalyst and noble metal catalyst series connection use, and both can reduce naphthalene the first step hydrogenation cost, and can improve again the purity of the finished product perhydronaphthalene.
3) naphthalene transformation efficiency is high, side reaction is few, perhydronaphthalene purity is high, adopt the inventive method, the transformation efficiency > 99.9% of naphthalene, perhydronaphthalene selectivity > 99, perhydronaphthalene total recovery > 94.5%, product purity > 99%.
Accompanying drawing explanation
The process flow diagram of Fig. 1 to be NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of the present invention be raw material continuous seepage perhydronaphthalene.
In figure: 1 raw material mixing tank, 2 one-stage hydrogenation reactors, 3 gas-liquid separator I, 4 scrubber towers, 5 second-stage hydrogenation reactors, 6 gas-liquid separator II, 7 product rectifying tower.
Embodiment
Below in conjunction with Figure of description and embodiment, the processing method to NAPTHALENE FLAKES. (INDUSTRIAL GRADE） continuous seepage perhydronaphthalene of the present invention is further elaborated.
Shown in the process flow diagram of NAPTHALENE FLAKES. (INDUSTRIAL GRADE） continuous seepage perhydronaphthalene as of the present invention in Fig. 1, first NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and solvent are mixed in proportion in raw material mixing tank 1, mix with hydrogen afterwards and be heated to temperature of reaction and enter one-stage hydrogenation reactor 2, hydrogenation products is after gas-liquid separator I3 is separated, and gas-phase product removes H through scrubber tower 4
2s and NH
3use Deng hydrogen recycle after impurity.A liquid product part returns raw material mixing tank 1 as solvent, liquid product another part enters second-stage hydrogenation reactor 5, and reaction product is after gas-liquid separator II6, and hydrogen recycle uses, liquid phase enters product rectifying tower 7, removes after a small amount of light constituent obtain high purity perhydronaphthalene through rectifying.
Embodiment 1
Take naphthalene content as the NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of 95% be raw material, naphthane and perhydronaphthalene mixture are solvent, NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and solvent volume are than being 1:5, the nickel-alumina catalyst of one-stage hydrogenation reactor charge 100mLNCG-6 (Catalyst Plant, SINOPEC Najing Chemical Industry Co., Ltd's production), temperature of reaction 230 DEG C, reaction pressure 5MPa, liquid hourly space velocity 1.8h
-1, gas-liquid volume ratio 800:1.Second-stage hydrogenation reactor filling 100mL platinum Al catalysts (China Patent Publication No.: CN1457923), temperature of reaction 200 DEG C, reaction pressure 10MPa, liquid hourly space velocity 0.3h
-1, gas-liquid volume ratio 600:1.The transformation efficiency of naphthalene is 99.9%, the selectivity 99% of perhydronaphthalene, and perhydronaphthalene total recovery reaches 94.5%, and product purity is 99%.
Embodiment 2
Take naphthalene content as the NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of 95% be raw material, naphthane and perhydronaphthalene mixture are solvent, NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and solvent volume are than being 1:5, one-stage hydrogenation reactor charge 100mL nickel-alumina catalyst (China Patent Publication No.: CN1082388), temperature of reaction 280 DEG C, reaction pressure 3MPa, liquid hourly space velocity 2.0h
-1, gas-liquid volume ratio 800:1.Second-stage hydrogenation reactor filling 100mL platinum catalyst (China Patent Publication No.: CN102836737), temperature of reaction 220 DEG C, reaction pressure 10MPa, liquid hourly space velocity 0.3h
-1, gas-liquid volume ratio 600:1.The transformation efficiency of naphthalene is 99.92%, the selectivity 99.3 of perhydronaphthalene, and perhydronaphthalene total recovery reaches 94.7%, and product purity is 99%.
Claims (1)
1. NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is a processing method for raw material continuous seepage perhydronaphthalene, it is characterized in that, comprises the following steps:
1) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and solvent with the volume ratio of 1:1 ~ 10 after raw material mixing tank mixes, mixing with hydrogen and entering one-stage hydrogenation reactor hydrogenation reaction after being heated to temperature of reaction, hydrogenation products is after gas-liquid separator separates, gas-phase product through scrubber tower removing impurities matter obtain hydrogen recycle use, liquid product a part as solvent refluxing to raw material mixing tank; Wherein said one-stage hydrogenation reaction conditions is: reaction pressure 1 ~ 5MPa, temperature of reaction, and hydrogen liquid volume ratio 100 ~ 1000:1, liquid hourly space velocity counts 0.1 ~ 5h with NAPTHALENE FLAKES. (INDUSTRIAL GRADE）
-1, catalyzer is the non-precious metal catalyst of desulfurization, denitrogenation and hydrogenating function, in simple substance, and metalloid content 10wt% ~ 50wt%, described one-stage hydrogenation reactor is isothermal shell and tube reactor;
2) another part liquid product enters the further hydrogenation reaction of second-stage hydrogenation reactor, and reaction product is after gas-liquid separator, and hydrogen recycle uses, and liquid phase enters product rectifying tower, removes after a small amount of light constituent obtain high purity perhydronaphthalene through rectifying; Wherein said secondary hydrogenation reaction conditions is: reaction pressure 5 ~ 20MPa, temperature of reaction 200 ~ 400 DEG C, hydrogen liquid volume ratio 100 ~ 1000:1, liquid hourly space velocity 0.1 ~ 5h
-1, catalyzer adopts the noble metal catalyst of high hydrogenation activity, and in simple substance, bullion content is content 0.05wt% ~ 5wt%, and described second stage reactor is heat-insulating fixed-bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610080521.1A CN105541542A (en) | 2016-02-04 | 2016-02-04 | Technique for continuously producing decahydronaphthalene from industrial naphthalene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610080521.1A CN105541542A (en) | 2016-02-04 | 2016-02-04 | Technique for continuously producing decahydronaphthalene from industrial naphthalene |
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| CN201610080521.1A Pending CN105541542A (en) | 2016-02-04 | 2016-02-04 | Technique for continuously producing decahydronaphthalene from industrial naphthalene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108059581A (en) * | 2016-11-09 | 2018-05-22 | 上海宝钢化工有限公司 | Method for preparing tetrahydronaphthalene by naphthalene hydrogenation |
| CN114011428A (en) * | 2021-12-07 | 2022-02-08 | 太原理工大学 | Catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene and preparation method thereof |
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| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| CN1733663A (en) * | 2005-08-10 | 2006-02-15 | 中国石油化工集团公司 | Decahydronaphthalene continuous hydrogenation synthesis method |
| CN102836737A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Naphthalene hydrogenation catalyst and preparation method thereof |
| CN104744203A (en) * | 2015-03-18 | 2015-07-01 | 大连理工大学 | Method for preparing decahydronaphthalene by virtue of industrial naphthalene hydrogenation |
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2016
- 2016-02-04 CN CN201610080521.1A patent/CN105541542A/en active Pending
Patent Citations (4)
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| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| CN1733663A (en) * | 2005-08-10 | 2006-02-15 | 中国石油化工集团公司 | Decahydronaphthalene continuous hydrogenation synthesis method |
| CN102836737A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Naphthalene hydrogenation catalyst and preparation method thereof |
| CN104744203A (en) * | 2015-03-18 | 2015-07-01 | 大连理工大学 | Method for preparing decahydronaphthalene by virtue of industrial naphthalene hydrogenation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108059581A (en) * | 2016-11-09 | 2018-05-22 | 上海宝钢化工有限公司 | Method for preparing tetrahydronaphthalene by naphthalene hydrogenation |
| CN108059581B (en) * | 2016-11-09 | 2021-04-02 | 宝武炭材料科技有限公司 | Method for preparing tetrahydronaphthalene by naphthalene hydrogenation |
| CN114011428A (en) * | 2021-12-07 | 2022-02-08 | 太原理工大学 | Catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene and preparation method thereof |
| CN114011428B (en) * | 2021-12-07 | 2024-05-03 | 太原理工大学 | Catalyst for preparing decalin by naphthalene one-step hydrogenation and preparation method thereof |
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Application publication date: 20160504 |