CN105237373A - Method for preparing MIBK through industrial by-product low-purity acetone - Google Patents
Method for preparing MIBK through industrial by-product low-purity acetone Download PDFInfo
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- CN105237373A CN105237373A CN201510671332.7A CN201510671332A CN105237373A CN 105237373 A CN105237373 A CN 105237373A CN 201510671332 A CN201510671332 A CN 201510671332A CN 105237373 A CN105237373 A CN 105237373A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/73—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
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Abstract
The invention discloses a method for preparing MIBK through industrial by-product low-purity acetone. The method is performed through two segments of technologies. In the first segment of technology, acetone is converted into MIBK and part of impurities under the action of MIBK synthetic catalysts; in the second segment of technology, under the action of protective catalysts, main impurities are converted into products easy to separate and it is guaranteed that acetone is not lost basically. The method can achieve conversion of most part of substances difficult to separate in raw material, products are easy to eliminate through rectification, reaction temperature of a main reaction catalyst bed layer is remarkably lowered, the service life of main catalysts is remarkably prolonged, unexpected side reaction is inhibited, and therefore the product yield and the economical efficiency of a device are further improved. MIBK superior products with the purity being 99.5wt% can be obtained by separating reaction products.
Description
Technical field
The present invention relates to the preparation method of a kind of MIBK (methyl iso-butyl ketone (MIBK)), be specifically related to a kind of method utilizing industrial by-product low-purity acetone to prepare MIBK, belong to organic synthesis field.
Background technology
Methyl iso-butyl ketone (MIBK) (MIBK) is a kind of important organic solvent, mainly as one of raw material producing rubber antioxidant, can be used for the dewaxing of paint waxy oil, cold coating, also the solvent producing tsiklomitsin, penicillin can be used as, in oil refining, as oil dewaxing agent, for the production of Refined Paraffin Wax, it is of many uses.
In industrial production MIBK method, there are acetone three-step approach, acetone through one-step method and Virahol single stage method.Acetone three-step approach is the main production before the seventies, technology maturation, DAA (diacetone alcohol), MO (mesityl oxide) can be produced according to the market requirement, but due to this complex process, flow process is longer, investment is comparatively large, and production cost is high, restricts further developing of this technique.The reaction conditions of Virahol single stage method is gentle, but by product is more, and energy consumption is high.Acetone through one-step method synthesis MIBK needs elevated pressures, and require higher to the resistance to hydrogen-type corrosion of equipment, therefore facility investment is higher simultaneously; But because acetone through one-step method by product is few, transformation efficiency and selectivity higher, separating device will be less than Virahol single stage method, and therefore, the production of current MIBK is mainly based on acetone through one-step method.
The raw material that the processing method of acetone through one-step method synthesis MIBK adopts is pure acetone, as Chinese publication CN00110591.4, CN95120403.3, CN1951893A, it is raw material One-step production MIBK that CN102050713A and CN03145566.2 etc. all disclose with pure acetone, used catalyst is Pd/ resin catalyst, this catalyzer is that Pd load is on Zeo-karb, there is the function of condensation dehydration and hydrogenation simultaneously, wherein hydrogenating function is provided by Pd, acid required for condensation dehydration is provided by the sulfonic acid group on Zeo-karb, two kinds of active centre need coupling appropriate, if hydrogenation activity is not enough, have MO in product to generate, the boiling point (128 DEG C) of MO differs less with the boiling point (116 DEG C) of MIBK, point defection of later stage MO affects the quality of MIBK product, if hydrogenation activity is higher, raw material acetone very easily direct hydrogenation generates Virahol.In reaction process, Pd and sulfonic acid group all have leakage, and this is also the principal phenomena affecting catalyst life.In addition, the heat resistance of resin catalyst is poor, and temperature SC service ceiling is generally 120 DEG C, and the loss of the higher sulfonic acid group of temperature also can be accelerated, and the use temperature causing catalyzer is limited.Simultaneously after 2010, acetone price, always at 5000 yuan/t-10000 unit/t, causes MIBK production cost larger by the impact of acetone price.
A large amount of low-purity acetone of existing industrial by-product are not fully utilized, and treatment process has 1) outside sell as fuel, 2) outside sell as usual vehicle.China publication CN201410128345 discloses a kind of method being prepared high-purity MIBK by industrial by-product waste liquid acetone, makes industrial by-product low-purity acetone obtain certain utilization.Adopt the Pd-resin catalyst of modification, by the catalyst hydrogenation technology of advanced person, adopt single stage method to prepare high-purity MIBK by industrial by-product waste liquid acetone, realize the Efficient Conversion of acetone to MIBK.But because the major impurity in industrial by-product waste liquid acetone is epoxy Trimethylmethane, epoxy Trimethylmethane is easy to tautomerize to isobutyric aldehyde, but the boiling point of isobutyric aldehyde and acetone closely, so isobutyric aldehyde easily in later separation along with acetone recycle accumulation, impact enters the acetone purity of reactor, and then affects the selectivity of acetone conversion and MIBK.
Improve catalyst resin carrier in China publication CN201410128345, adopt resistant to elevated temperatures matrix or introduce resistant to elevated temperatures group, realizing impurity epoxy Trimethylmethane Efficient Conversion is the follow-up isopropylcarbinol being easy to be separated.But be also conducive to the generation of some side reactions under high temperature, reduce the yield of target product, have impact on device economy.Show the long period experiment of above-mentioned technique, the coming off of active group of resin catalyst is an inevitable process, and under the high temperature more than 130 DEG C, long-term operation catalyzer still has inactivation to a certain degree simultaneously.In addition catalyzer manufacturing cost is high, and the use cost of catalyzer is still very high.
Therefore, farthest effectively utilizing to realize industrial by-product low-purity acetone, effectively can improve the competitive power of MIBK product simultaneously, reduce the production cost of product, need to find a kind of new processing method, realize efficiently preparing high-purity MIBK by industrial by-product low-purity acetone.
Summary of the invention
The object of this invention is to provide a kind of method being prepared MIBK (methyl iso-butyl ketone (MIBK)) by industrial by-product low-purity acetone; adopt two-stage process; by adding guard catalyst to MIBK preparation process amelioration; realize impurity conversion be easy to be separated isopropylcarbinol while; acetone as far as possible not hydrogenation generate Virahol, and the temperature of MIBK synthesis reactor can be reduced significantly, reduce side reaction; extend the work-ing life of MIBK synthetic catalyst, and then improve the economic benefit of device further.
For reaching above goal of the invention, the technical solution used in the present invention is as follows:
Prepared a method of MIBK by industrial by-product low-purity acetone, carry out with two-stage process:
First paragraph technique, under catalyst action, the acetone conversion in by-product low-purity acetone is MIBK, and the yield that the epoxy Trimethylmethane in impurity is converted into isopropylcarbinol is 1 ~ 30%, and preferably epoxy Trimethylmethane is converted into the yield of isopropylcarbinol is 3 ~ 15%; And
Second segment technique, under guard catalyst effect, the yield that the epoxy Trimethylmethane in impurity is converted into isopropylcarbinol is 30 ~ 95%, is preferably 60 ~ 90%, and acetone conversion is the yield of Virahol is simultaneously 0.05 ~ 1%.
In the present invention, described primary industry by-product low-purity acetone is without separating-purifying, and the impurity in industrial by-product low-purity acetone is including but not limited to epoxy Trimethylmethane, methyl alcohol, the trimethyl carbinol, Virahol, water, t-butyl formate etc.; Wherein, in the total mass of by-product low-purity acetone, the content of acetone is 60 ~ 95wt%, and the content of epoxy Trimethylmethane is 1 ~ 20wt%.
In the present invention, in first paragraph technique, described catalyzer can be the catalyzer for MIBK synthesis known at present, and also can be through the high temperature resistant Pd-resin catalyst of resin improved, described catalyzer has the several functions such as condensation, dehydration and shortening; Described catalyzer includes but not limited to Pd-resin compounded catalyzer, Pd-ZSM-5 composite catalyst, Pd/Al
2o
3catalyzer or Ni/Al
2o
3catalyzer; Preferred Pd-resin compounded catalyzer.
In the present invention, the purity of first paragraph technique and second segment technique hydrogen used is 99.9 ~ 99.99wt%.
In the present invention, in first paragraph technique, hydrogenation reaction temperature is 80 ~ 150 DEG C, preferably 90 ~ 130 DEG C; Reaction pressure (gauge pressure) is 0.1 ~ 7MPa, and be preferably 0.1 ~ 3MPa, the feed volume air speed of by-product low-purity acetone is 0.5 ~ 2h
-1, preferably 0.8 ~ 1.5h
-1; Hydrogen-oil ratio is 0.1 ~ 1, preferably 0.3 ~ 0.7; Wherein, hydrogen-oil ratio refers to the mol ratio of acetone in hydrogen and initial by-product low-purity acetone.
In the present invention, described by-product low-purity acetone and hydrogen are successively by first paragraph technique and second segment technique, under catalyst action, acetone hydrogenation is converted into MIBK, major impurity simultaneously in waste liquid acetone is converted into segregative isopropylcarbinol, reaction product obtains MIBK product through rectifying separation, realizes the recycling of unconverted acetone simultaneously.
In order to prevent, temperature of reaction is too high, catalyst deactivation is very fast in the present invention, acetone hydrogenation is avoided to generate by product Virahol, by the control of the reaction conditionss such as the temperature to first paragraph technique, pressure, hydrogen-oil ratio, realize controlling the yield spectra that impurity epoxy Trimethylmethane is converted into isopropylcarbinol.The present invention is converted into the yield of isopropylcarbinol by controlling impurity epoxy Trimethylmethane in first paragraph technique; then can by using guard catalyst in second segment technique; control the reaction conditions etc. of second segment technique simultaneously; thus final realization efficiently prepares high-purity MIBK by industrial by-product low-purity acetone, reaction effect is made to reach best.
In the present invention, the guard catalyst described in second segment technique is one or two or more in load type palladium, supported copper catalyst and non-loading type copper catalyst, preferred non-loading type copper catalyst.
Described in second segment technique of the present invention, guard catalyst specific surface area is 80 ~ 500m
2/ g, preferably 120 ~ 220m
2/ g, pore volume is 0.1 ~ 0.5cm
3/ g, preferably 0.2 ~ 0.4cm
3/ g, aperture is
preferably
In the present invention, the carrier of described load type palladium catalyst is gac or aluminum oxide, preferred gac, and based on the total mass of described loaded palladium catalyst, the content of palladium is 0.3% ~ 8%, is preferably 3% ~ 6%.
In the present invention, the structure of described supported copper catalyst is Cu-A/B, wherein B is carrier, A is auxiliary agent, described carrier is intermediate oxide, be preferably the one or two or more of aluminum oxide, beryllium oxide, zinc oxide, tindioxide, zirconium dioxide and titanium dioxide etc., more preferably zirconium dioxide and/or titanium dioxide, more preferably titanium dioxide.Described auxiliary agent is the one or two or more in zinc, tin, lead and bismuth, preferred zinc and/or tin.Based on the total mass of copper-loading catalyst, the massfraction of Cu is 6% ~ 55%, preferably 9% ~ 39%; The massfraction of A is 0.01% ~ 40%; The massfraction of B is 40% ~ 90%, preferably 45% ~ 80%.
In the present invention, titanium dioxide is as the carrier B of supported copper catalyst in second segment technique, be embodied in titanium dioxide containing a large amount of Lewis acid, catalyzer is when carrying out reduction activation simultaneously, carrier titanium dioxide surface can be reduced the Lewis acid position of the electron deficiency of formation, be conducive to the O atom polarized in C=O key, thus improve catalyzer to the ability of C=O key selective hydrogenation, simultaneously by adding auxiliary agent zinc, tin, plumbous, bismuth etc., catalyzer makes a small amount of active ingredient copper and auxiliary agent form Cu-A alloy while reduction activation, thus it is active to acetone hydrogenation to reduce catalyzer, further increase the selectivity of catalyzer to impurity hydrogenation, it be the yield of Virahol is 0.05 ~ 1% that the yield that improve isopropylcarbinol can realize controlling acetone conversion simultaneously.
In the present invention, the structure of described non-loading type copper catalyst is Cu-A-C, and wherein A is auxiliary agent, and C is water-resisting agent.Based on the total mass of unsupported copper catalyst, the content of Cu is 5% ~ 65%, preferably 9% ~ 60%; The content of A is 30% ~ 90%, preferably 34% ~ 85%; The content of C is 0.005% ~ 10%.A is Zn and is selected from one or two or more in Al, Si, Mg, Fe, Ni, Ca, Zr, Ti, Co and K, and preferably, based on the total mass of A, wherein the content of Zn is 30 ~ 60%, Al is 0 ~ 30%, Si is 0 ~ 30%, all the other are 0 ~ 10%; C is silicone based water-resisting agent, the one or two or more in preferred alkyl silicates, silicane, silicon resin solution and resin emulsion, more preferably alkyl silicic acids salt.
In the present invention; controlled by the content of active ingredient copper and auxiliary agent Zn etc. to non-loading type copper guard catalyst in second segment technique; thus reach the activity and optionally object that regulate catalyzer; realizing impurity epoxy Trimethylmethane, to be converted into the yield of isopropylcarbinol higher, and acetone conversion is that the yield of Virahol controls to be 0.05 ~ 1% simultaneously.Because the water tolerance of copper zinc catalyst is poor, the present invention, after copper catalyst is shaping, is coated with one deck water-resisting agent C by spraying process at catalyst surface, thus improves the water tolerance of catalyzer, the life-span of extending catalyst.
In the present invention, the reaction of second segment technique can be gas-phase reaction also can be liquid phase reaction, and preferred liquid phase is reacted.Temperature of reaction is 40 ~ 180 DEG C, preferably 50 DEG C ~ 150 DEG C.The reaction pressure of second segment technique can be high pressure also can be low pressure, can be identical with the reaction pressure of first paragraph technique, also can be different, preferably identical with the reaction pressure of first paragraph technique, and reaction pressure (gauge pressure) is preferably 0.1 ~ 3MPa.Hydrogen-oil ratio and the first paragraph technique of second segment technique are identical or different, preferably identical with the hydrogen-oil ratio of first paragraph technique, are 0.1 ~ 1, are preferably 0.3 ~ 0.7; Wherein, hydrogen-oil ratio refers to the mol ratio of acetone in hydrogen feed amount and initial by-product low-purity acetone.In the present invention, first paragraph technique and second segment technique are carried out respectively in the first reactor and the second reactor, or carry out in first reaction zone and second reaction zone of same reactor.
In the present invention, when first paragraph technique and second segment technique are carried out respectively in the first reactor and the second reactor, first reactor and the second reactor are flow reactor, can be the same or different, be respectively fixed-bed tube reactor or continuous stirred tank reactor, preferably two reactors are identical, are fixed-bed tube reactor.The entrance and exit of two reactors all fills inert material, and wherein said inert material is inert alumina, pottery, glass filler, Pall ring etc., and the thickness of inert material bed is 10 ~ 200cm, preferably 20 ~ 100cm.Feed mode can be all upper feeding pattern or lower feed mode, and the first reactor is the operation of upper feeding pattern, and the second reactor is the operation of lower feed mode, and the first reactor is the operation of lower feed mode, and the second reactor is the operation of upper feeding pattern.Unreacted acetone can loop back the first reactor by rectifying and continue reaction.
In the present invention, when first paragraph technique and second segment technique are carried out in first reaction zone and second reaction zone of same reactor, described reactor is tubular reactor, described reactor inlet, between the first reaction zone and second reaction zone and reactor outlet all fill inert material, make the first reaction zone and second reaction zone separated from one another, wherein said inert material is inert alumina, pottery, glass filler, Pall ring etc., the thickness of inert material bed is 10 ~ 200cm, preferably 20 ~ 100cm.Feed mode can be upper feeding pattern also can be the operation of lower feed mode, and preferred upper feeding pattern, reactor inlet uses liquid dispenser.Unreacted acetone can loop back the first reaction zone by rectifying and continue reaction.
In the present invention, by introducing second segment technique, significantly can relax the reaction conditions of MIBK synthesis reactor, reducing reaction pressure, thus adjustment reaction conditions is to being more conducive to the scope improving MIBK yield.The impurity fully do not transformed in first process section; react fully in second segment technique; simultaneously; by to the guard catalyst in second segment technique; the yield making impurity epoxy Trimethylmethane be converted into isopropylcarbinol reaches 30% ~ 90%; and the side reaction that acetone conversion is Virahol also can be inhibited; thus control composition and the content of reactor outlet impurity, avoid difficult separate substance to refine in downstream and cause impurities accumulation finally to affect the normal operation of complete assembly with acetone recycle to reactor in recover acetone operation.
In the present invention second process section, the yield that impurity epoxy Trimethylmethane is converted into isopropylcarbinol close to 100%, but can be considered for economy, is generally recommended as 60 ~ 90%.
In the present invention, the Reactive Synthesis liquid of two-stage process carries out rectification and purification through cut light tower, recover acetone tower, dehydration tower, dealcoholize column and MIBK treating tower successively.Cut light tower operates under the condition of the preferred 100 ~ 200KPa of pressure 5 ~ 300KPa; Theoretical plate number is 5 ~ 60, preferably 15 ~ 50; Feed entrance point is 10-30 plate, preferred 15-25 plate.Recover acetone tower is the conditional operation of 50 ~ 100KPa at pressure; Theoretical plate number is 10 ~ 100, preferably 30 ~ 60; Feed entrance point is 10 ~ 35 plates, preferably 15 ~ 25 plates.Dehydration tower is 50 ~ 500KPa, preferably 100 ~ 260KPa at pressure; Theoretical plate number is 10 ~ 60, preferably 15 ~ 50; Feed entrance point is 10 ~ 30 plates, preferably 10 ~ 25 plates.Operating under pressure is 100 ~ 250KPa condition of dealcoholize column; Theoretical plate number is 15 ~ 55; Feed entrance point is 15 ~ 25 blocks of plates.MIBK treating tower is 5 ~ 200KPa at pressure, preferably operates under 100 ~ 180KPa condition; Theoretical plate number 20 ~ 60, preferably 30 ~ 50; Feed entrance point is 10 ~ 40 plates, preferably 15 ~ 20 plates.The MIBK product that massfraction is 99.5%-99.8% is obtained by refining.
The Reactive Synthesis liquid of two-stage process of the present invention is after rectification and purification, and the MIBK product purity obtained can reach 99.5 ~ 99.8wt%.
Beneficial effect of the present invention is:
1, adopt two-stage process, Controlling Technology parameter, realize while impurity conversion is the isopropylcarbinol being easy to be separated, and acetone as far as possible not hydrogenation generate Virahol, extend the work-ing life of MIBK synthetic catalyst, improve the economic benefit of device further.
2, the introduction of guard catalyst in second segment technique, reduces the temperature of MIBK synthesis reactor, improves product selectivity.While obtaining MIBK product, in raw material, most of light constituent is converted into and is easy to separate substance, effectively controls the side reaction of acetone, and whole technique is more simple.
3, solve the re-using problem of industrial by-product low-purity acetone, avoid wastage of material, achieve and transformed to the MIBK with high added value by low-purity acetone.Relative to traditional preparation methods, possess significant raw materials cost advantage, then coordinate the rectification flow of optimization, recoverable acetone and the highly purified MIBK product of preparation, make device possess very strong economic competitiveness.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of employing two reactors
Fig. 2 is the process flow diagram adopting two reaction zones
Embodiment
The present invention combines embodiment below and is described in further detail, but scope of the present invention is not limited to these embodiments.
Gas-chromatography: Shimadzu model GC2010-plus, chromatographic column HP-PONA (50m × 0.2mm × 0.25 μm), injector temperature 230 DEG C, heating schedule: 40 DEG C, keep 8 minutes, 10 DEG C/min is warming up to 240 DEG C; Detector temperature is 300 DEG C.
AmberlystCH-28, DOW Chemical company limited, wherein Pd content is 0.7wt%;
D5H5A, auspicious section, wherein Pd content is 5wt%,
In each embodiment, the composition of raw materials used by-product low-purity acetone is as shown in table 1:
Table 1 raw material by-product low-purity acetone forms
| Composition wt% | Embodiment three, four | Embodiment five, six | Embodiment seven, eight | Embodiment nine | Comparative example |
| Water | 0.78 | 0.53 | 0.25 | 1.54 | 0.78 |
| Methyl alcohol | 3.09 | 8.25 | 2.41 | 0.75 | 3.09 |
| Acetone | 87.01 | 60 | 95.00 | 78.00 | 87.01 |
| Virahol | 0.03 | 0.04 | 0.02 | 0.13 | 0.03 |
| Epoxy Trimethylmethane | 6.30 | 20 | 1.00 | 10.00 | 6.30 |
| The trimethyl carbinol | 1.59 | 5.89 | 0.64 | 4.36 | 1.59 |
| Trimethylmethane | 1.20 | 5.29 | 0.68 | 5.22 | 1.20 |
As shown in Figure 1: raw material, fresh hydrogen and circulating hydrogen enter the first reactor, after reaction, acetone conversion is MIBK; After reaction, hydrogen and reacted liquid enter the second reactor respectively, and after the second reactor, impurity is further converted to isopropylcarbinol, and unreacted hydrogen recycle uses, and synthesis liquid enters follow-up rectification flow.
As shown in Figure 2: raw material, fresh hydrogen and circulating hydrogen enter the first reaction zone and second reaction zone successively, realizing acetone conversion is that MIBK and epoxy Trimethylmethane are converted into segregative isopropylcarbinol.
Embodiment one
The preparation of non-loading type copper catalyst Cu-1, Cu-2 and Cu-3 in the guard catalyst that second segment technique uses:
By Cu (NO
3)
23H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o, Ca (NO
3)
24H
2o, Mg (NO
3)
26H
2o, Fe (NO
3)
39H
2o respectively in the ratio wiring solution-forming 1 of 9:75:40:15:10:2,35:55:25:8:15:1,60:36:26:4:0.61:0.15, solution 2 and solution 3, respectively to wherein slowly dripping Na
2cO
3the aqueous solution, control rate of addition make its pH remain on 4 ~ 6, after treating that coprecipitation reaction completes, at room temperature aging 12 ~ 24h; Vacuum filtration will precipitate and be separated with mother liquor afterwards, and precipitate with a large amount of deionized water rinsings in the process of suction filtration; Dry 8 ~ 12h at being deposited in 80 ~ 100 DEG C, then at N
2roasting 4h at lower 400 DEG C of atmosphere; Extrusion molding afterwards, and the ethanol-water solution containing 1% commercial KP-853 water-resisting agent is sprayed on catalyst surface, drying at room temperature 20 ~ 24h by the method that the catalyzer after shaping is sprayed, the non-loading type copper catalyst that surface scribbles water-resisting agent can be obtained.
Wherein Cu massfraction be 9% catalyzer be denoted as Cu-1 catalyzer, Cu massfraction be 35% catalyzer be denoted as Cu-2 catalyzer, Cu massfraction be 60% catalyzer be denoted as Cu-3 catalyzer.
Embodiment two
The preparation of supported copper catalyst Cu-Sn-1, Cu-Sn-2 and Cu-Sn-3 in the guard catalyst that second segment technique uses:
By CuCl
22H
2o and SnCl
45H
2o adds in the stearic acid of melting respectively by certain mass ratio, in 80 ~ 100 DEG C of magnetic agitation 6 ~ 8h, to be drained off completely after add a certain amount of butyl (tetra) titanate violent stirring 3 ~ 5h back cover and form translucent colloidal sol, at 100 DEG C after dry 4 ~ 6h in retort furnace 400 DEG C ~ 500 DEG C roasting 2 ~ 4h, under 350 ~ 400 DEG C of hydrogen atmospheres, reduce 4 ~ 6h afterwards.
According to aforesaid method finally obtained m (Cu): m (Sn): m (TiO
2) be the Catalysts Cu-Sn-1 of 9:11:80, obtained m (Cu): m (Sn): m (TiO
2) be the Catalysts Cu-Sn-2 of 25:5:70, obtained m (Cu): m (Sn): m (TiO
2) be the Catalysts Cu-Sn-3 of 39:16:45.
Embodiment three
Raw material composition is as shown in table 1, and the catalyzer of the first process section is AmberlystCH-28, and reactor is fixed-bed reactor, and temperature of reaction is 100 DEG C, and reaction pressure is 3MPa, and hydrogen-oil ratio (mol ratio) is 0.7, and air speed is 1h
-1.The catalyzer of the second process section adopts auspicious section D5H5A, and reactor is continuous stirred tank reactor (CSTR), and temperature of reaction is 125 DEG C, and reaction pressure is 3MPa, and reactor volume is 2L, and catalyst levels is 5g, and the residence time is 30min.
The reaction product gathering first paragraph technique and second segment technique carries out stratographic analysis, and concrete outcome lists in table 2.
Reaction result after table 2 two-stage process
As can be seen from Table 2: when only having a segment process, the yield of isopropylcarbinol only has 9.84%, and epoxy Trimethylmethane major part transforms in order to isobutyric aldehyde, and isobutyric aldehyde is separated with acetone is more difficult, affects the separation of subsequent product.After adding second segment reaction process, main reaction temperature is when lesser temps, also can realize most of epoxy Trimethylmethane by second segment technique and be converted into isopropylcarbinol, and the selectivity of isopropylcarbinol is up to 95.00%, ensure the high conversion of acetone and the highly selective of MIBK, acetone conversion is that the yield of Virahol is only 0.13% simultaneously.
The reaction product generated in second segment technique is carried out atmospheric distillation, filler adopts the triangle spiral of Ф 3 × 3, and post height 1m overhead condensation water temp is 25 DEG C, when tower top temperature is 51 DEG C ~ 53 DEG C, reflux ratio is the azeotrope of 5:1, overhead extraction 2-MP, acetone and ethers etc.; When tower top temperature is 57 DEG C ~ 59 DEG C, reflux ratio is 2:1, and overhead extraction is the components such as acetone, methyl alcohol, isobutyric aldehyde; Residue tower bottoms is carried out separatory, and get upper oil phase and continue rectifying, when tower top temperature is 87 DEG C ~ 107 DEG C, reflux ratio is 5:1, the azeotrope of the azeotrope of overhead extraction water and MIBK, Virahol and isopropylcarbinol and MIBK; Tower top temperature is 116 ~ 117 DEG C, reflux ratio 5:1, overhead extraction MIBK sample, high purity 99.8wt%.
Embodiment four
Raw material composition is as shown in table 1, and the catalyzer of the first process section is AmberlystCH-28, and wherein Pd content is 0.7%, and reactor adopts fixed-bed reactor, and temperature of reaction is 90 DEG C, and reaction pressure is 3MPa, and air speed is 1h
-1, hydrogen-oil ratio (mol ratio) is 0.6.The catalyzer of the second process section adopts unsupported Cu-1 catalyzer, and reactor is fixed-bed reactor, and temperature of reaction is 150 DEG C, and reaction pressure is 0.3MPa, air speed 5h
-1, hydrogen-oil ratio (mol ratio) is 0.1.And first paragraph technique and second segment technique are carried out respectively in different reactors, the fed version of this two-stage process is all upper feeding, and reactor inlet and reactor outlet are equipped with the inert alumina bead of 40cm respectively.
The reaction product gathering first paragraph technique and second segment technique carries out stratographic analysis, and concrete reaction result lists in table 3.
The reaction product generated in second segment technique is carried out atmospheric distillation, filler adopts the triangle spiral of Ф 3 × 3, and post height 1m overhead condensation water temp is 25 DEG C, when tower top temperature is 51 DEG C ~ 53 DEG C, reflux ratio is the azeotrope of 5:1, overhead extraction 2-MP, acetone and ethers etc.; When tower top temperature is 57 DEG C ~ 59 DEG C, reflux ratio is 2:1, and overhead extraction is the components such as acetone, methyl alcohol, isobutyric aldehyde; Residue tower bottoms is carried out separatory, and get upper oil phase and continue rectifying, when tower top temperature is 87 DEG C ~ 107 DEG C, reflux ratio is 5:1, the azeotrope of the azeotrope of overhead extraction water and MIBK, Virahol and isopropylcarbinol and MIBK; Tower top temperature is 116 ~ 117 DEG C, reflux ratio 5:1, overhead extraction MIBK sample, high purity 99.8%.
Embodiment five
Raw material composition is as shown in table 1, and the catalyzer of the first process section adopts AmberlystCH-28, and wherein Pd content is 0.7%, and reactor adopts fixed-bed reactor, and temperature of reaction is 110 DEG C, and reaction pressure is 2MPa, and air speed is 1h
-1, hydrogen-oil ratio (mol ratio) is 0.3.The catalyzer of the second process section adopts unsupported Cu-2 catalyzer, and reactor is fixed-bed reactor, and temperature of reaction is 100 DEG C, and reaction pressure is 2MPa, air speed 1h
-1, hydrogen-oil ratio (mol ratio) is 0.3.And first paragraph technique is carried out in identical reactor with second segment technique, the fed version of this two-stage process is all upper feeding, and the inert alumina bead of 20cm is housed between reactor inlet, reactor outlet and two-stage process respectively.
The reaction product gathering second segment technique carries out stratographic analysis, the results are shown in table 3.
Embodiment six
Raw material composition is as shown in table 1, the catalyzer of the first process section adopt AmberlystCH-28 wherein Pd content be 0.7%, reactor adopts fixed-bed reactor, and temperature of reaction is 130 DEG C, and reaction pressure is 2MPa, and air speed is 1.5h
-1, hydrogen-oil ratio (mol ratio) is 0.5.The catalyzer of the second process section adopts unsupported Cu-3 catalyzer, and reactor is fixed-bed reactor, and temperature of reaction is 50 DEG C, and reaction pressure is 0.1MPa, air speed 1h
-1, hydrogen-oil ratio (mol ratio) is 0.7.And first paragraph technique and second segment technique are carried out in not identical reactor, the fed version of this two-stage process is all lower charging, and reactor inlet and reactor outlet are equipped with the inert alumina bead of 40cm respectively.
The reaction product gathering second segment technique carries out stratographic analysis, and concrete reaction result lists in table 3.
Reaction result after table 3 two-stage process
As can be seen from Table 3: most of epoxy Trimethylmethane can be realized by second segment technique in embodiment four, five, six and be converted into isopropylcarbinol, and the selectivity of isopropylcarbinol is respectively up to 81.11%, 90.00% and 60.00%, ensure the high conversion of acetone and the highly selective of MIBK, acetone conversion is that the yield of Virahol is respectively 0.58%, 0.05% and 0.50% simultaneously.
Embodiment seven
Raw material is as shown in table 1.The catalyzer of the first process section adopts high-temperature catalyst-3 disclosed in CN201410128345, and technology disclosed in preparation process reference CN200610045641, reactor adopts fixed-bed reactor, and temperature of reaction is 110 DEG C, and reaction pressure is 3MPa, and air speed is 1.2h
-1, hydrogen-oil ratio (mol ratio) is 0.6.The catalyzer of the second process section adopts Cu-Sn-1 catalyzer, and reactor is fixed-bed reactor, and temperature of reaction is 50 DEG C, and reaction pressure is 3MPa, air speed 1.2h
-1, hydrogen-oil ratio (mol ratio) is 0.6.And first paragraph technique and second segment technique are carried out in the differential responses district of same reactor, and fed version is upper feeding, and the inert alumina bead of 20cm is housed between reactor inlet, reactor outlet and two-stage process respectively.The reaction product gathering second segment technique carries out stratographic analysis, the results are shown in table 4.
Embodiment eight
Raw material is as shown in table 1.The catalyzer of the first process section adopts high-temperature catalyst-4 disclosed in CN201410128345, and technology disclosed in preparation process reference CN200610045641, reactor adopts fixed-bed reactor, and temperature of reaction is 130 DEG C, and reaction pressure is 3MPa, and air speed is 1.2h
-1, hydrogen-oil ratio (mol ratio) is 0.6.The catalyzer of the second process section adopts Cu-Sn-2 catalyzer, and reactor is fixed-bed reactor, and temperature of reaction is 120 DEG C, and reaction pressure is 3MPa, air speed 2h
-1, hydrogen-oil ratio (mol ratio) is 0.6.And first paragraph technique and second segment technique are carried out in different reactor, fed version is all lower charging, and reactor inlet and reactor outlet are equipped with the inert alumina bead of 40cm respectively.The reaction product gathering first paragraph technique and second segment technique carries out stratographic analysis, the results are shown in table 4.
Embodiment nine
Raw material is as shown in table 1.The catalyzer of the first process section adopts AmberlystCH-28, and wherein Pd content is 0.7%, and reactor adopts fixed-bed reactor, and temperature of reaction is 110 DEG C, and reaction pressure is 0.1MPa, and air speed is 1.2h
-1, hydrogen-oil ratio (mol ratio) is 0.6.The catalyzer of the second process section adopts Cu-Sn-3 catalyzer, and reactor is fixed-bed reactor, and temperature of reaction is 60 DEG C, and reaction pressure is 3MPa, air speed 5h
-1, hydrogen-oil ratio (mol ratio) is 0.6.And first paragraph technique and second segment technique are carried out in different reactor, fed version is upper feeding, and reactor inlet and reactor outlet are equipped with the inert alumina bead of 40cm respectively.The reaction product gathering first paragraph technique and second segment technique carries out stratographic analysis, the results are shown in table 4.
Reaction result after table 4 two-stage process
As can be seen from Table 4: most of epoxy Trimethylmethane can be realized by second segment technique and be converted into isopropylcarbinol, and the selectivity of isopropylcarbinol is respectively up to 75.00%, 81.00% and 30.00%, ensure the high conversion of acetone and the highly selective of MIBK, acetone conversion is that the yield of Virahol is respectively 0.23%, 1% and 0.13% simultaneously.
Comparative example 1 and comparative example 2
In comparative example 1 and comparative example 2, MIBK Reactive Synthesis catalyzer adopts fire resistant resin catalyzer-3 disclosed in ROHM AND HAAS macropore ion-exchange green resin Amb-36 and CN201410128345 respectively, the palladium content of both difference load 0.7wt%, 24h is boiled, technology disclosed in the catalyst preparation process reference CN200610045641 of carrying metal palladium in 160 DEG C of pressure distillation water.Reactor inside diameter Ф 20, adopts multistage heating formula heat-insulation system; Catalyzer is the spherical particle of Ф 0.3 ~ 1.3, amount of fill 100ml; By-product acetone mixture and hydrogen also flow through beds.Collection liquid sample analysis, concrete reaction conditions and the results are shown in table 5.
When table 5 low temperature and high temperature, different catalysts is synthesized MIBK and is contrasted
Note: ethers comprises diisopropyl ether, two tertiary butyl ether, methyl isobutylether, methyl tert-butyl ether etc.Drawn by table 5: under pyroreaction, epoxy Trimethylmethane major part can be converted into the isopropylcarbinol being easy to be separated, but the selectivity of MIBK is lower only 78.85% and 69.59%.
Claims (9)
1. prepared a method of MIBK by industrial by-product low-purity acetone, carry out with two-stage process:
First paragraph technique, under catalyst action, the acetone conversion in by-product low-purity acetone is MIBK, and the yield that the epoxy Trimethylmethane in impurity is converted into isopropylcarbinol is 1 ~ 30%; Preferably epoxy Trimethylmethane is converted into the yield of isopropylcarbinol is 3 ~ 15%; And
Second segment technique, under guard catalyst effect, the yield that the epoxy Trimethylmethane in impurity is converted into isopropylcarbinol is 30 ~ 95%, is preferably 60 ~ 90%, and acetone conversion is the yield of Virahol is simultaneously 0.05 ~ 1%.
2. method according to claim 1, is characterized in that, guard catalyst described in second segment technique is the one or two or more in load type palladium catalyst, supported copper catalyst and non-loading type copper catalyst, preferred non-loading type copper catalyst.
3. method according to claim 2, is characterized in that, the carrier of described load type palladium catalyst is gac or aluminum oxide, preferred gac; Based on the total mass of load type palladium catalyst, the massfraction of Pd is 0.3% ~ 8%, preferably 3% ~ 6%;
The structure of described supported copper catalyst is Cu-A/B, and described A is the one or two or more in zinc, tin, lead and bismuth, is preferably zinc and/or tin; B is intermediate oxide carrier, is preferably the one or two or more in aluminum oxide, beryllium oxide, zinc oxide, tindioxide, zirconium dioxide and titanium dioxide, is more preferably zirconium dioxide and/or titanium dioxide, further preferred titanium dioxide; Based on the total mass of supported copper catalyst, the massfraction of Cu is 6% ~ 55%, preferably 9% ~ 39%; The massfraction of A is 0.01% ~ 40%; The massfraction of B is 40% ~ 90%, is preferably 45% ~ 80%;
The structure of described non-loading type copper catalyst is Cu-A-C, and based on the total mass of unsupported copper catalyst, the massfraction of Cu is 5% ~ 65%, preferably 9% ~ 60%; The massfraction of A is 30% ~ 90%, preferably 34% ~ 85%; The massfraction of C is 0.005% ~ 10%; Wherein A is auxiliary agent, the one or two or more that A is Zn and is selected from Al, Si, Mg, Fe, Ni, Ca, Zr, Ti, Co and K, preferably, based on the total mass of auxiliary agent A, the massfraction of Zn is 30 ~ 60%, Al is 0 ~ 30%, Si is 0 ~ 30%, and all the other are 0 ~ 10%; C is silicone based water-resisting agent, the one or two or more in preferred alkyl silicates, silicane, silicon resin solution and resin emulsion, more preferably alkyl silicic acids salt.
4. the method according to any one of claim 1-3, is characterized in that, the volume space velocity of the acetone of by-product low-purity described in second segment technique is 0.5 ~ 10h
-1, preferably 1 ~ 5h
-1.
5. the method according to any one of claim 1-4, it is characterized in that, impurity in described industrial by-product low-purity acetone comprises epoxy Trimethylmethane, methyl alcohol, the trimethyl carbinol, Virahol, water and t-butyl formate, in the total mass of by-product low-purity acetone, wherein, the content of acetone is 60 ~ 95wt%, and the content of epoxy Trimethylmethane is 1 ~ 20wt%.
6. the method according to any one of claim 1-5, is characterized in that, in first paragraph technique, hydrogenation reaction temperature is 80 ~ 150 DEG C, preferably 90 ~ 130 DEG C; Reaction pressure gauge pressure is 0.1 ~ 7MPa, is preferably 0.1 ~ 3MPa; Hydrogen-oil ratio is 0.1 ~ 1, is preferably 0.3 ~ 0.7; The feed volume air speed of by-product low-purity acetone is 0.5 ~ 2h
-1, preferably 0.8 ~ 1.5h
-1; Wherein, hydrogen-oil ratio refers to the mol ratio of acetone in hydrogen feed amount and initial by-product low-purity acetone.
7. the method according to any one of claim 1-6, is characterized in that, the temperature of reaction of second segment technique is 40 ~ 180 DEG C, preferably 50 DEG C ~ 150 DEG C; The reaction pressure gauge pressure of second segment technique is 0.1 ~ 3MPa; Hydrogen-oil ratio is 0.1 ~ 1, is preferably 0.3-0.7; Wherein, hydrogen-oil ratio refers to the mol ratio of acetone feed amount in hydrogen feed amount and initial by-product low-purity acetone.
8. method according to claim 1, is characterized in that, the catalyzer described in first paragraph technique is Pd-resin compounded catalyzer, Pd-ZSM-5 composite catalyst, Pd/Al
2o
3catalyzer or Ni/Al
2o
3catalyzer, is preferably Pd-resin compounded catalyzer.
9. the method according to any one of claim 1 ~ 8, is characterized in that, first paragraph technique and second segment technique are carried out respectively in the first reactor and the second reactor, or carries out in first reaction zone and second reaction zone of same reactor respectively; Described first reactor and the second reactor identical or different, be separately fixed-bed tube reactor or continuous stirred tank reactor (CSTR), preferably two reactors are identical, are fixed-bed tube reactor.
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| CN109718786A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of catalyst and its preparation method and application preparing methyl iso-butyl ketone (MIBK) and diisobutyl ketone for condensation of acetone |
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