CN1534031A - Catalytic distillation method of olefine direct epoxidation - Google Patents
Catalytic distillation method of olefine direct epoxidation Download PDFInfo
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Abstract
A catalytic distiling process for directly epoxidating olefine features that a tower which is vertically and sequentially divided into distilling segment, reaction segment and desorption segment is only used, and includes reacting between olefine, hydrogen peroxide, solvent and Ti-Si molecular sieve catalyst, condensing the excessive solvent and olefine and returning them back to reaction segment, and separating product from the substance discharged from tower bottom. Its advantages are high thermal efficiency and less energy consumption.
Description
Technical field
The present invention relates to a kind of under the katalysis of HTS, alkene and hydrogen peroxide initial ring oxidizing reaction, highly selective generates the method for organic epoxide.
Background technology
Typical large organic epoxide is oxyethane, propylene oxide and epoxy chloropropane, and they all are broad-spectrum basic Organic Chemicals.For oxyethane, the catalytic ethene of silver catalyst of existing main production method excellent property and the direct epoxidised technology of oxygen gas phase, this Technology economy advanced person, production process is pollution-free substantially.For propylene oxide, existing production method mainly contains chlorohydrination and conjugated oxidation, and wherein chlorohydrination material consumption and energy consumption height, equipment corrosion are serious, disposal of three wastes cost height; And conjugated oxidation, though solved corrosion and pollution problem, technology is more complicated, Technological Economy often is difficult to obtain good economic benefit because of the restriction of co-product purposes and market capacity.For epoxy chloropropane, existing production method mainly contains propenyl chloride method and two kinds of technologies of vinyl carbinol method.Since all contain the chlorohydrination process in these two kinds of technologies, thereby exist by product many, the material consumption height, energy consumption is big, and seriously corroded is administered defectives such as the three wastes have high input, and the Technological Economy of technology is very poor, and environmental protection pressure is big.
In order to solve the traditional technology problem, late 1980s, US4833260 discloses the direct process for epoxidation of a kind of alkene, and it is catalyzer with the HTS, directly alkene is carried out epoxidation with hydrogen peroxide, optionally generates epoxide.The reaction equation of this process (this reaction is thermopositive reaction, and Q represents heat) as follows:
Although the selectivity ratios that should react is higher, because the existence of strong polar compound such as water or alcohol in the reaction system, ring-opening reaction will take place in the epoxide of generation on catalyzer top, reduce the selectivity of epoxide.For this reason, US4824976 and CN1319099A propose to handle catalyzer with suitable acid neutralizing agent before reaction or in reaction process, exist on the catalyst neutralisation surface, open loop plays the acidic-group of katalysis to epoxide, to reach the purpose that suppresses epoxide open loop side reaction.The alkaline matter of mentioning in these patents can be the water-soluble alkaline material, for example alkali such as sodium hydroxide, potassium hydroxide, ammoniacal liquor; The aqueous solution such as yellow soda ash, sodium bicarbonate and sodium hydrogen phosphate and similar potassium and lithium salts are the salt of alkalescence; The aqueous solution be carboxy acid alkali's metal of alkalescence and/or alkaline earth salt and basic metal and or alkaline-earth alkoxides; Also have tertiary amine or tertiary amino oxides etc.Afterwards, US5646314 and US5675026 reported again, and some non-basic salt is the selectivity that neutral salt or acid-salt such as lithium chloride, sodium sulfate, lithium nitrate, magnesium acetate and ammonium acetate can improve the epoxidation reaction of titanium molecular sieve catalysis equally.But the adding of these materials causes adverse influence to the aftertreatment of product, some material even can bring the fouling and the etching problem of equipment.
In the alkene hydrogen dioxide epoxidation reaction system of titanium molecular sieve catalysis, catalyst Ti-si molecular sieves is a solid, and alkene and hydrogen peroxide are dissolved in simultaneously and contact with catalyzer with liquid form in a kind of solvent and react.Because exothermic heat of reaction is big, and hydrogen peroxide invalid decomposition when temperature surpasses 100 ℃ will aggravate, and therefore, than higher, reactor becomes the key equipment of this reaction process to this reaction system to the requirement of reactor.EP0659473A1 is disclosed to be a kind of trickle bed reaction process, catalyzer divides four sections to be filled in the trickle-bed reactor with oarse-grained form, intersegmental riser and the liquid collecting plate of being provided with, first three section of lathe bed is the main reaction section, indirect cooler of every section peripheral hardware is with heat-obtaining.Epoxidation reaction with propylene is an example, under the reaction pressure more than the 1.25MPa, the mode that reaction mass is gas-liquid two-phase and stream is flowed downward and is reacted by the bed top, on the main reaction section, reaction mixture is carried out extraction, heat exchange, returned and replenish reinforced process, be that the reacted reactant of each section is after an indirect cooler cooling, a part loops back this section, and another part and fresh feed are mixed into next section.In order to improve the transformation efficiency of hydrogen peroxide, the feed liquid that enters the 4th section does not add fresh feed, product and tail gas by bed at the bottom of extraction.This reactor structure complexity, the working pressure height, temperature is controlled and is relied on the realization of systemic circulation material, need also after reaction finishes that solvent is evaporated separation and recycle with realization, so energy consumption is very high.
CN1256273A discloses a kind of continuous slurry circulation reaction process, (median size is that 0.1～200nm) HTS is a catalyzer with fine particle for it, catalyzer is dispersed in the reaction feed liquid mobile with the form of slurry attitude, and the direct epoxidation of catalyzing propone and hydrogen peroxide generates propylene oxide simultaneously.Its reactor mainly constitutes based on the tubular reaction section of reacting, a shell and tube cooling section and the gas-liquid separation section based on heat exchange by one.Tubular reaction section and cooling section are put side by side, and two ends communicate with the U-shaped pipe coupling up and down, form a loop, connect gas-liquid separator in the upper end of shell and tube cooling section.For ensureing that sufficient reacting carries out, the tubulation length-to-diameter ratio that requires conversion zone to adopt is 10: 1～200: 1, is provided with sparger on the tubulation termination up and down at conversion zone, to promote mixing of feed liquid and catalyzer.According to the introduction of this patent, this technology can realize the continuous epoxidation process of propylene and hydrogen peroxide, and temperature of reaction is easy to control, and catalyzer is convenient to change or regeneration, and the mol ratio of propylene/hydrogen peroxide is low in the charging, and working pressure is low.But the reaction unit complex structure of this technology, the energy consumption of solvent recuperation is big, and a large amount of reaction heat is not utilized effectively.
Summary of the invention
The purpose of this invention is to provide the direct epoxidised catalytic distillation method of a kind of alkene, to overcome the shortcoming of above-mentioned prior art.
Method provided by the invention comprises:
Method provided by the invention mainly is to carry out in a tower that is made of conversion zone, distilling period and/or stripping section, distilling period is positioned at the top of conversion zone, stripping section is positioned at the below of conversion zone, the conversion zone that alkene, hydrogen peroxide and solvent enter tower contacts with titanium-silicon molecular sieve catalyst and reacts, the solvent of vaporization returns conversion zone, and epoxide product obtains from cat head or the separation of tower still.
The present invention will react with separating to be placed in the same tower and carry out, and a large amount of reaction heat are directly used in evaporation and separate remaining reactants and solvent, and utilization of Heat of Reaction rate height do not need special heat-obtaining facility, thereby device construction is simple, and the energy consumption of production process reduces greatly.
Embodiment
Method provided by the invention mainly is to carry out in a tower that is made of conversion zone, distilling period and/or stripping section, and wherein distilling period is positioned at the top of conversion zone, and stripping section is positioned at the below of conversion zone.Described tower can be packing tower, sieve-tray tower, valve tray column, spray tower, grid tray tower of various types etc., and conversion zone, distilling period and stripping section can adopt the tower of same type to make up, and also can take dissimilar towers to make up.
The conversion zone that alkene, hydrogen peroxide and solvent enter tower contacts with titanium-silicon molecular sieve catalyst and reacts, and the solvent of vaporization returns conversion zone, and epoxide product separates from cat head or tower still and obtains.
Described alkene is selected from alkene, cycloolefin, haloolefin or a polyene hydrocarbon, preferably contains alkene, cycloolefin or the haloolefin of 3～18 carbon atoms, is more preferably propylene, propenyl chloride.They can be pure product, also can contain the material that some do not have a negative impact to epoxidation reaction and product separation.
Described hydrogen peroxide can be pure product, but considers from security standpoint, preferably uses the aqueous solution of hydrogen peroxide, and its concentration is 1%～99% preferred 20%～60%.
In general, the mutual solubility between alkene and the aqueous hydrogen peroxide solution is bad.Therefore, prior art all adds solvent in reaction system, as methyl alcohol, ethanol, propyl alcohol, acetone etc., promotes dissolving mutually between alkene and the aqueous hydrogen peroxide solution, reacts with the contact of solid catalyst helping.According to method provided by the invention, it also is necessary selecting these solvents for use, but unlike the prior art be, these solvents are except that the dissolving function, also additional important function, reaction heat is taken out in i.e. evaporation, has not only controlled temperature of reaction easily, and utilizes reaction heat that solvent is separated from reaction system.These solvents are selected from alcohol, ketone, acid, ester, and pure and mild 3～8 ketone that preferred carbon atoms is 1～8 is more preferably methyl alcohol, ethanol, propyl alcohol, butanols, acetone and methylethylketone etc.
Described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in the lattice framework.This class material is well known in the prior art, as the titanium-containing zeolite with the MFI topological framework that is similar to the ZSM-5 aluminosilicate zeolite be TS-1, titanium-containing zeolite with the MEL topological framework that is similar to the ZSM-11 aluminosilicate zeolite is TS-2 and has with the molecular sieve containing titanium of β zeolite, mordenite, ZSM-12, MCM-41 and ZSM-48 isomorphous skeleton structure etc., preferred TS-1 and TS-2.The used catalyzer of the present invention is directly processed by this molecular sieve analog, also can be by these molecular sieves by means manufacturings such as load or bondings.When the method for selecting bonding or load for use was made catalyzer, for fear of nonselective hydrogen peroxide decomposition of catalysis or epoxide ring-opening reaction, tackiness agent or carrier must be non-acid materials.Tackiness agent that can be used and carrier comprise titanium dioxide, silicon-dioxide, aluminum oxide and silica-alumina, silica-titania, silica-magnesia composite oxides etc., also have some non-acid clays if you would take off stone, kaolin, wilkinite and sepiolite etc., wherein the content of HTS is preferably in more than 5%, to guarantee catalyzer enough activity is arranged.Catalyzer can be seated in the tower with various forms of tying up bag, also can loose to pile up on the sieve plate in the sieve-tray tower.
In theory, 1 mole alkene complete reaction need consume 1 mole hydrogen peroxide.According to method provided by the invention, in order to improve the effective rate of utilization of hydrogen peroxide, it is necessary keeping in the tower conversion zone alkene excessive, therefore, the mol ratio of alkene and hydrogen peroxide should be 1～10 in the charging: 1, preferred 1.5～6: 1, the unreacted alkene Separation and Recovery, recycling.The mol ratio of conversion zone alkene and solvent can be selected between 1: 3～1: 20 in the tower, preferred 1: 5～1: 15.In the described reaction conditions, the scope of temperature of reaction is 40～100 ℃, and preferred 55～80 ℃, the reaction absolute pressure is 0.1～3MPa, preferred 0.1～1.0MPa; Mass space velocity is counted 0.05～10h with alkene during the liquid of charging
-1, be preferably 0.1～8h
-1
The reaction process that the method for employing catalytic distillation is carried out alkene epoxidation can have following several embodiment, but the present invention is not limited to this:
One of embodiment:
The alkene of, easy vaporization low for boiling point and the boiling point of product are lower than the system of temperature of reaction, alkene can divide one or more snippets lower end from conversion zone to enter the tower, oxidants hydrogen peroxide and solvent enter the tower from the upper end of conversion zone, mix mutually with the hydrogen peroxide and the solvent that descend in uphill process alkene vaporization back, contacts with catalyzer and react.Meanwhile, the reaction liberated heat makes the solvent vaporization, removes heat, has limited the rising of conversion zone temperature, thereby realizes shifting out the purpose of heat, control conversion zone temperature.Solvent recycles in conversion zone through fractionator at distilling period, and unreacted alkene enters with the product epoxide and recycles after condenser is told product.
Two of embodiment:
For boiling point than higher but be lower than the alkene of temperature of reaction, alkene, oxidants hydrogen peroxide and solvent enter from conversion zone upper end together and contact with catalyzer the tower and react, the reaction liberated heat makes the solvent vaporization, remove heat, keep the steady of conversion zone temperature, thereby realized shifting out the purpose of heat, control conversion zone temperature.The solvent and the unreacted alkene of vaporization enter conversion zone at distilling period through fractionator and recycle, and partial solvent and product enter stripping section, and solvent is steamed back conversion zone and continues use, and product epoxide, water and the by product that may generate are from the extraction of tower still.
Three of embodiment:
The alkene that is higher than temperature of reaction for boiling point, alkene, oxidants hydrogen peroxide and solvent enter from conversion zone upper end together and contact with catalyzer the tower and react, the reaction liberated heat makes the solvent vaporization, remove heat, keep the steady of conversion zone temperature, thereby realized shifting out the purpose of heat, control conversion zone temperature.The solvent of vaporization enters conversion zone at distilling period through fractionator and recycles, the unreacted alkene that enters stripping section with the product epoxide is steamed back the conversion zone continuation and is reacted in stripping section, product epoxide, water and the by product that may generate are from the extraction of tower still.
Method provided by the invention is applicable to the direct epoxidation reaction of alkene, haloolefin and other alkene, is specially adapted to the direct epoxidation reaction of propylene or propenyl chloride and hydrogen peroxide.
The advantage of this technology is in particular in: (1) adopts the direct epoxidation of hydrogen peroxide, has fundamentally solved heavy corrosion and pollution problem that chlorohydrination technology exists; (2), hindered the side reaction that product takes place effectively, thereby improved the selectivity of epoxide because the epoxide that reaction generates has in time shifted out reaction zone; (3) adopt the solvent evaporation heat-obtaining, prevent device reaction section temperature runaway, prevented the hydrogen peroxide thermolysis effectively, hydrogen peroxide utilization ratio height; (4) reaction is carried out with separating to be coupling in the tower, and flow process is simple, reduces investment outlay; (5) epoxidation process a large amount of reaction heat of emitting are directly used in evaporation and are separated remaining reactants and solvent, and utilization of Heat of Reaction rate height need special heat-obtaining facility, thereby device construction is simple, and the energy consumption of production process reduces greatly.
The following examples will give further instruction to present method, but therefore not limit present method.
The used titanium-silicon molecular sieve catalyst trade mark is HTS among the embodiment, builds feldspar oiling worker limited-liability company by the Hunan and produces.Test is carried out in an internal diameter is the glass tower of 34mm, and catalyzer is piled up conversion zone in tower with the form of tying up bag by layer, all fills the porcelain rings with φ 3 * 6mm in distilling period and the stripping section.Distance between the opening for feed is 1000mm up and down, and the height of conversion zone, distilling period and stripping section is set according to concrete reaction, and body of the tower is with the insulation of mineral wool electric heating blanket parcel, and the tower still adopts the electric heating temperature control, the logical tap water cooling of overhead condenser.The composition gas chromatographic analysis of sample, the remnants iodimetric analysis of hydrogen peroxide.The charging mole number of unit time hydrogen peroxide is with n
0Expression, remaining mole number is with n
rExpression, the mole number that generates epoxide is with n
EExpression, then
The transformation efficiency of hydrogen peroxide=[(n
0-n
r)/n0] * 100%
The epoxidised selectivity of hydrogen peroxide=[n
E/ (n
0-n
r)] * 100%
Embodiment 1
This embodiment is a propylone direct opoxidation system propylene oxide.
Reaction raw materials is 27% industrial hydrogen peroxide, the industry of the polymerization-grade more than 99.9% propylene, and solvent is an analytical pure methyl alcohol.Hydrogen peroxide opening for feed from the conversion zone of tower is squeezed into conversion zone the tower by volume pump, and the following opening for feed from conversion zone after the mass flowmeter metering of the propylene behind the pressure reducing flow stable enters the tower, and the mol ratio of propylene and hydrogen peroxide is 2.5: 1.After device is opened, at first squeeze into methyl alcohol from the epimere of conversion zone, treat device running steadily after, advance propylene and hydrogen peroxide, replenish methyl alcohol simultaneously, be 1: 8 up to the mol ratio of conversion zone propylene and methyl alcohol.Reaction conditions is as follows: the conversion zone temperature is controlled at 60 ℃, reaction pressure 0.12MPa (absolute pressure), propylene mass space velocity 1.25h
-1Propylene is while dissolving and hydroperoxidation in the tower, the reaction liberated heat makes the propylene oxide vaporization of methyl alcohol and generation, enter the distilling period fractionation with the remaining propylene of reaction, methanol eddy enters conversion zone again, propylene oxide and propylene enter condenser from the cat head distilling period, the preliminary condensation separation of propylene oxide quilt, the emptying behind the propylene oxide that further low temperature separation process goes out to carry secretly of remaining gas.The water that reaction generates and enter the tower still with the water that hydrogen peroxide is brought reactive system into.Reaction result: hydrogen peroxide conversion is 99%, and the epoxidised selectivity of hydrogen peroxide is 95.5%.
Embodiment 2
This embodiment is a propylone direct opoxidation system propylene oxide.
Reaction raw materials and solvent are with embodiment 1.4: 1 in molar ratio ratio charging of propylene, hydrogen peroxide, the mol ratio of conversion zone propylene and methyl alcohol is 1: 12.Reaction conditions is: the conversion zone temperature is controlled at 70 ℃, reaction pressure 0.2MPa (absolute pressure), propylene mass space velocity 3.5h
-1Process operation is with embodiment 1.Reaction result: hydrogen peroxide conversion is 100%, and the epoxidised selectivity of hydrogen peroxide is 97.3%.
Embodiment 3
This embodiment is the direct epoxidation system epoxy chloropropane of propenyl chloride.
Reaction raw materials is industrial goods, and wherein the purity of hydrogen peroxide is 50%, and the purity of propenyl chloride is 97.0%; Solvent is an analytical pure methyl alcohol.After device is opened, at first be that 1: 9 ratio is squeezed in the tower in molar ratio with propenyl chloride and methyl alcohol, treat device running steadily after, throw hydrogen peroxide into, additional simultaneously methyl alcohol and propenyl chloride are 1: 9 up to the mol ratio of conversion zone propenyl chloride and methyl alcohol.Hydrogen peroxide and methyl alcohol opening for feed from the conversion zone of tower is squeezed into by volume pump, and propenyl chloride enters the tower from the following opening for feed of conversion zone, and the mol ratio of control conversion zone propenyl chloride and hydrogen peroxide is 2: 1.Reaction conditions is as follows: the conversion zone temperature is controlled at 60 ℃, reaction pressure 0.15MPa (absolute pressure), propenyl chloride mass space velocity 4.5h
-1Propenyl chloride and hydroperoxidation liberated heat make methyl alcohol and the vaporization of unreacted propenyl chloride, enter distilling period together, and methyl alcohol and propenyl chloride are back to conversion zone and participate in reaction again, remaining tail gas emptying.Epoxy chloropropane, water and part methyl alcohol enter stripping section, propose methyl alcohol and enter conversion zone, and epoxy chloropropane, water enter the tower still.Reaction result: hydrogen peroxide conversion is 100%, and the epoxidised selectivity of hydrogen peroxide is 95.7%.
Embodiment 4
This embodiment is the direct epoxidation system epoxy chloropropane of propenyl chloride.
Reaction raw materials is industrial goods, and wherein the purity of hydrogen peroxide is 27%, and the purity of propenyl chloride is 97.0%; Solvent is an analytical pure acetone.After device is opened, the ratio that at first with propenyl chloride and acetone is 1: 10 is in molar ratio squeezed in the tower, after treating device running steadily, throw hydrogen peroxide into, replenish acetone and propenyl chloride simultaneously, mol ratio up to conversion zone propenyl chloride and acetone is 1: 10, and the mol ratio of propenyl chloride and hydrogen peroxide is 1.5: 1.Reaction conditions is as follows: the conversion zone temperature is controlled at 80 ℃, reaction pressure 0.2MPa (absolute pressure), propenyl chloride mass space velocity 2h
-1Propenyl chloride makes solvent and the vaporization of unreacted propenyl chloride enter distilling period with the hydroperoxidation liberated heat, and acetone and propenyl chloride are back to conversion zone and participate in reaction again, the tail gas emptying.Epoxy chloropropane, water and part acetone enter stripping section, propose acetone and enter conversion zone, and epoxy chloropropane, water enter the tower still.Reaction result: hydrogen peroxide conversion is 100%, and the epoxidised selectivity of hydrogen peroxide is 97.8%.
Claims (11)
1, the direct epoxidised catalytic distillation method of a kind of alkene, it is characterized in that conversion zone that alkene, hydrogen peroxide and solvent enter tower contacts with titanium-silicon molecular sieve catalyst and reacts, the solvent of vaporization returns conversion zone, and epoxide product obtains from cat head or the separation of tower still.
2, according to the method for claim 1, it is characterized in that described tower is made of conversion zone, distilling period and/or stripping section, distilling period is positioned at the top of conversion zone, and stripping section is positioned at the below of conversion zone,
3,, it is characterized in that described alkene is alkene, cycloolefin, haloolefin or a polyene hydrocarbon according to the method for claim 1.
4,, it is characterized in that described alkene is alkene, cycloolefin or the haloolefin that contains 3～18 carbon atoms, is more preferably propylene, propenyl chloride according to the method for claim 1 or 3.
5,, it is characterized in that described alkene is propylene, propenyl chloride according to the method for claim 1 or 3.
6,, it is characterized in that described solvent is alcohol, ketone, acid, ester according to the method for claim 1.
7,, it is characterized in that described solvent is the ketone that contains pure and mild 3～8 carbon atoms of 1～8 carbon atom according to the method for claim 1 or 6.
8, according to the method for claim 1, the mol ratio that it is characterized in that alkene and hydrogen peroxide is 1～10: 1.
9, according to the method for claim 1 or 8, the mol ratio that it is characterized in that alkene and hydrogen peroxide is 1.5～6: 1.
10, according to the method for claim 1, the mol ratio that it is characterized in that conversion zone alkene and solvent is 1: 3～1: 20, and temperature of reaction is 40～100 ℃, and the reaction absolute pressure is 0.1～3MPa, and mass space velocity is counted 0.05～10h with alkene during the liquid of charging
-1
11, according to the method for claim 1 or 10, the mol ratio that it is characterized in that conversion zone alkene and solvent is 1: 5～1: 15, and temperature of reaction is 55～80 ℃, and the reaction absolute pressure is 0.1～1.0MPa, and to count with alkene be 0.1～8h to mass space velocity during the liquid of charging
-1
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Cited By (11)
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| WO2011012869A3 (en) * | 2009-07-31 | 2011-05-05 | South Bank University Enterprises Ltd | Process |
| CN102190637A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Production method of epichlorohydrin |
| CN102190635A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Method for producing epoxy chloropropane |
| CN102260226A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Olefin epoxidation method |
| CN102372683A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing epichlorohydrin through chloropropene epoxidation |
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| CN109748887A (en) * | 2017-11-08 | 2019-05-14 | 中国石油化工股份有限公司 | The method of controlling security of HPPO technique hydrogen peroxide charging |
| CN111606871A (en) * | 2020-05-25 | 2020-09-01 | 中国科学院理化技术研究所 | Preparation method of epichlorohydrin |
| CN111606871B (en) * | 2020-05-25 | 2022-04-15 | 中国科学院理化技术研究所 | Preparation method of epichlorohydrin |
| CN114380773A (en) * | 2022-01-19 | 2022-04-22 | 中国五环工程有限公司 | Process for producing epoxypropane by reactive distillation |
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