CN105237373B - 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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- CN105237373B CN105237373B CN201510671332.7A CN201510671332A CN105237373B CN 105237373 B CN105237373 B CN 105237373B CN 201510671332 A CN201510671332 A CN 201510671332A CN 105237373 B CN105237373 B CN 105237373B
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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 a kind of preparation method of MIBK (methyl iso-butyl ketone (MIBK)), and in particular to one kind is low using industrial by-product
The method that purity acetone prepares MIBK, belongs to organic synthesis field.
Background technology
Methyl iso-butyl ketone (MIBK) (MIBK) is a kind of important organic solvent, mainly as production rubber antioxidant raw material it
One, can be used to paint content of wax oil dewaxing, cold coating, it is also possible to the solvent as production tetracycline, penicillin, in oil refining,
Used as oil dewaxing agent, for producing fully refined paraffin wax, its is of many uses.
In commercial production MIBK method, there are acetone three-step approach, acetone through one-step method and isopropanol one-step method.Acetone three-step approach is
Main production before the seventies, technology maturation can be according to market demand production DAA (DAA), MO (isopropylidenes third
Ketone), but due to the complex process, flow process is longer, invests larger, and production cost is high, restricts the further development of the technique.Isopropyl
The reaction condition of alcohol one-step method is gentle, but by-product is more, high energy consumption.Acetone through one-step method synthesis MIBK needs elevated pressures, together
When, requires the resistance to hydrogen-type corrosion of equipment higher, therefore equipment investment is higher；But due to acetone through one-step method by-product it is few, conversion ratio and
Selectivity is higher, and separation equipment will be less than isopropanol one-step method, therefore, the production of current MIBK is mainly with acetone through one-step method
It is main.
The raw material that adopts of process of acetone through one-step method synthesis MIBK for pure acetone, such as China's publication
CN00110591.4, CN95120403.3, CN1951893A, CN102050713A and CN03145566.2 etc. disclose with
Pure acetone is raw material One-step production MIBK, and used catalyst is Pd/ resin catalysts, and the catalyst is that Pd is supported on cation
On exchanger resin, while with condensation dehydration and the function being hydrogenated with, wherein hydrogenating function is provided by Pd, required for condensation dehydration
Acid is provided by the sulfonic acid group on cation exchange resin, and two kinds of active center need matching appropriate, if hydrogenation activity is not enough,
MO generations are had in product, the boiling point (128 DEG C) of MO differs less with the boiling point of MIBK (116 DEG C), the separation of later stage MO can shadow
Ring the quality of MIBK products；If hydrogenation activity is higher, raw material acetone easily direct hydrogenation generates isopropanol.During the course of the reaction
Pd and sulfonic acid group have leakage, and this is also the principal phenomena for affecting catalyst life.Additionally, resin catalyst
Heat resistance 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 cause catalysis
The use of agent is temperature limited.Simultaneously after 2010, acetone price in 5000 yuan/t-10000 units/t, causes MIBK to produce always
Cost is affected larger by acetone price.
A large amount of low-purity acetone of existing industrial by-product are not fully utilized, and processing method has outside 1) sells as fuel,
2) sell as usual vehicle outside.Chinese publication CN201410128345 discloses a kind of by the preparation of industrial by-product waste liquid acetone
The method of high-purity MIBK, makes industrial by-product low-purity acetone obtain certain utilization.Using modified Pd- resin catalysts,
By advanced catalyst hydrogenation technology, high-purity MIBK is prepared by industrial by-product waste liquid acetone using one-step method, realize that acetone is arrived
The Efficient Conversion of MIBK.But because the major impurity in industrial by-product waste liquid acetone is epoxy iso-butane, epoxy iso-butane holds very much
Isobutylaldehyde is easily tautomerized to, but the boiling point of isobutylaldehyde and acetone is closely, so isobutylaldehyde is easily in later separation with third
Ketone circulation accumulation, affects the acetone purity into reactor, and then affects the selectivity of acetone conversion and MIBK.
Catalyst resin carrier is improved in Chinese publication CN201410128345, using resistant to elevated temperatures base
Body introduces resistant to elevated temperatures group, realizes that impurity epoxy iso-butane Efficient Conversion is the isobutanol being subsequently easily isolated.But it is high
The generation of some side reactions is also beneficial under temperature, the yield of target product is reduced, device economy is have impact on.Simultaneously to above-mentioned
The long period experiment of technique shows that coming off for the active group of resin catalyst is an inevitable process, more than 130 DEG C
At a high temperature of, long-term operation catalyst still has a certain degree of inactivation.In addition catalyst manufacturing cost is high, and catalyst makes
It is still very high with cost.
Therefore, in order to realize the maximum effectively utilizes of industrial by-product low-purity acetone, while MIBK can be effectively improved
The competitiveness of product, reduces the production cost of product, needs to find a kind of new process, realizes by industrial by-product low-purity
Acetone efficiently prepares high-purity MIBK.
The content of the invention
It is an object of the invention to provide one kind is prepared the side of MIBK (methyl iso-butyl ketone (MIBK)) by industrial by-product low-purity acetone
Method, using two-stage process, by adding guard catalyst to MIBK preparation process ameliorations, realizes that impurity is converted into what is be easily isolated
While isobutanol, acetone is not hydrogenated to isopropanol as far as possible, and can significantly reduce the temperature of MIBK synthesis reactor, reduces
Side reaction, extends the service life of MIBK synthetic catalysts, and then further improves the economic benefit of device.
To reach above goal of the invention, the technical solution used in the present invention is as follows：
A kind of method for preparing MIBK by industrial by-product low-purity acetone, is carried out with two-stage process：
First segment process, under catalyst action, the acetone conversion in by-product low-purity acetone be MIBK, the ring in impurity
Oxygen iso-butane be converted into isobutanol yield be 1~30%, preferably epoxy iso-butane be converted into isobutanol yield be 3~
15%；And
Second segment process, under guard catalyst effect, the epoxy iso-butane in impurity is converted into the yield of isobutanol and is
30~95%, preferably 60~90%, while acetone conversion is 0.05~1% for the yield of isopropanol.
In the present invention, the primary industry by-product low-purity acetone is without separating-purifying, industrial by-product low-purity third
Impurity in ketone is including but not limited to epoxy iso-butane, methanol, the tert-butyl alcohol, isopropanol, water, t-butyl formate etc.；Wherein, with pair
The gross mass meter of low-purity acetone is produced, the content of acetone is 60~95wt%, and the content of epoxy iso-butane is 1~20wt%.
In the present invention, in the first segment process, the catalyst can be the catalyst for MIBK synthesis being currently known,
Can also be high temperature resistant Pd- resin catalyst improved through resin, the catalyst has condensation, dehydration and catalytic hydrogenation etc.
Several functions；The catalyst includes but is not limited to Pd- resin compounded catalyst, Pd-ZSM-5 composite catalysts, Pd/Al2O3Urge
Agent or Ni/Al2O3Catalyst；It is preferred that Pd- resin compounded catalyst.
In the present invention, the first segment process and purity of hydrogen is 99.9~99.99wt% used by the second segment process.
In the present invention, hydrogenation reaction temperature is 80~150 DEG C, preferably 90~130 DEG C in the first segment process；Reaction pressure
(gauge pressure) is 0.1~7MPa, preferably 0.1~3MPa, and 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 hydrogen with initial by-product low-purity acetone
The mol ratio of middle acetone.
In the present invention, the by-product low-purity acetone passes sequentially through the first segment process and the second segment process with hydrogen, is urging
Under agent effect, acetone hydrogenation is converted into MIBK, while the major impurity in waste liquid acetone is converted into segregative isobutanol,
The rectification of product Jing is separated and obtains MIBK products, while realizing the recycling of unconverted acetone.
Reaction temperature is too high, catalyst inactivation is very fast to prevent for the present invention, it is to avoid acetone hydrogenation generates by-product isopropanol,
By the control of the reaction conditions such as the temperature to the first segment process, pressure, hydrogen-oil ratio, the iso-butane conversion of control impurity epoxy is realized
For the yield spectra of isobutanol.The present invention is converted into the receipts of isobutanol by impurity epoxy iso-butane in the first segment process of control
Rate, then can by guard catalyst used in the second segment process, while control reaction condition of the second segment process etc., from
And finally realize efficiently preparing high-purity MIBK by industrial by-product low-purity acetone, reaction effect is reached most preferably.
In the present invention, the guard catalyst described in the second segment process is load type palladium, supported copper catalyst and non-negative
One or two or more in load type copper catalyst, preferred non-loading type copper catalyst.
Guard catalyst specific surface area is 80~500m described in second segment process of the invention2/ g, preferably 120~220m2/
G, pore volume is 0.1~0.5cm3/ g, preferably 0.2~0.4cm3/ g, aperture isIt is preferred that
In the present invention, the carrier of the load type palladium catalyst is activated carbon or aluminium oxide, preferred activated carbon, based on described
The gross mass of loaded palladium catalyst, the content of palladium is 0.3%~8%, preferably 3%~6%.
In the present invention, the structure of the supported copper catalyst is Cu-A '/B, and wherein B is carrier, and A ' is auxiliary agent, described
Carrier is amphoteric oxide, preferably the one of aluminium oxide, beryllium oxide, Zinc Oxide, tin ash, zirconium dioxide and titanium dioxide etc.
Plant or two or more, more preferably zirconium dioxide and/or titanium dioxide, more preferably titanium dioxide.The auxiliary agent be zinc,
One or two or more in stannum, lead and bismuth, preferred zinc and/or stannum.Based on the gross mass of copper-loading catalyst, the quality of Cu
Fraction is 6%~55%, preferably 9%~39%；The mass fraction of A ' is 0.01%~40%；The mass fraction of B be 40%~
90%, preferably 45%~80%.
In the present invention, titanium dioxide is embodied in titanium dioxide as the carrier B of supported copper catalyst in the second segment process
In containing substantial amounts of Lewis it is sour, while catalyst is when reduction activation is carried out, carrier titanium dioxide surface can be reduced to be formed
The Lewis acid position of electron deficiency, is conducive to the O atom polarized in C=O keys, so as to improve catalyst to C=O key selective hydrogenations
Ability, while by addition auxiliary agent zinc, stannum, lead, bismuth etc., catalyst make while reduction activation a small amount of active ingredient copper with
Auxiliary agent forms Cu-A ' alloys, so as to reduce catalyst to acetone hydrogenation activity, further increases what catalyst was hydrogenated with to impurity
Selectivity, improves the yield of isobutanol while it is 0.05~1% to be capable of achieving to control the yield that acetone conversion is isopropanol.
In the present invention, the structure of the non-loading type copper catalyst is Cu-A-C, and wherein A is auxiliary agent, and C is waterproofing agent.Base
In the gross mass of unsupported copper catalyst, the content of Cu is 5%~65%, preferably 9%~60%；The content of A be 30%~
90%, preferably 34%~85%；The content of C is 0.005%~10%.A be Zn and selected from Al, Si, Mg, Fe, Ni, Ca, Zr,
One or two or more in Ti, Co and K, it is preferred that the content of the gross mass based on A, wherein Zn is for 30~60%, Al
0~30%, Si be 0~30%, remaining be 0~10%；C be silicone waterproofing agent, preferred alkyl silicic acids salt, silanes,
One or two or more in silicon resin solution and resin emulsion, more preferably alkyl silicic acids salt.
In the present invention, by the active ingredient copper and auxiliary agent to non-loading type copper guard catalyst in the second segment process
The content of Zn etc. is controlled, and so as to reach the active and selective purpose for adjusting catalyst, realizes impurity epoxy isobutyl
The yield that alkane is converted into isobutanol is higher, while acetone conversion is controlled to 0.05~1% for the yield of isopropanol.Because copper zinc is urged
The resistance to water of agent is poor, and the present invention applies one layer of waterproofing agent by spraying treatment after copper catalyst molding in catalyst surface
C, so as to improve the resistance to water of catalyst, extends the life-span of catalyst.
In the present invention, it can also be liquid phase reactor that the reaction of the second segment process can be gas phase reaction, preferred liquid phase reaction.
Reaction temperature is 40~180 DEG C, preferably 50 DEG C~150 DEG C.It can also be low that the reaction pressure of the second segment process can be high pressure
Pressure, can be identical with the reaction pressure of the first segment process, it is also possible to different, preferably identical with the reaction pressure of the first segment process,
Reaction pressure (gauge pressure) is preferably 0.1~3MPa,.The hydrogen-oil ratio of the second segment process is identical or different with the first segment process, preferably
It is identical with the hydrogen-oil ratio of the first segment process, it is 0.1~1, preferably 0.3~0.7；Wherein, hydrogen-oil ratio refer to hydrogen inlet amount with it is first
The mol ratio of acetone in beginning by-product low-purity acetone.In the present invention, the first segment process and the second segment process are respectively in the first reaction
Carry out in device and second reactor, or carry out in first reaction zone and second reaction zone of same reactor.
In the present invention, when the first segment process and the second segment process are carried out respectively in first reactor and second reactor,
First reactor and second reactor are flow reactor, can be the same or different, respectively fixed bed pipe reaction
Device or continuous stirred tank reactor, preferably two reactors are identical, are fixed-bed tube reactor.The entrance of two reactors
Inert material is filled with outlet, wherein the inert material is inert alumina, ceramics, glass filler, Pall ring etc., inertia
Material bed thickness is 10~200cm, preferably 20~100cm.Feed mode can all be upper feeding pattern or lower charging mould
Formula, first reactor is the operation of upper feeding pattern, and second reactor is the operation of lower feed mode, and first reactor is lower charging mould
Formula is operated, and second reactor is the operation of upper feeding pattern.Unreacted acetone can by rectification loop back first reactor after
Continuous reaction.
In the present invention, the first segment process and the second segment process are in first reaction zone and second reaction zone of same reactor
When carrying out, the reactor be tubular reactor, between the reactor inlet, the first reaction zone and second reaction zone and
Reactor outlet fills inert material, makes the first reaction zone and second reaction zone separated from one another, wherein the inert material is
Inert alumina, ceramics, glass filler, Pall ring etc., the thickness of inert material bed is 10~200cm, preferably 20~100cm.
It can also be lower feed mode operation that feed mode can be upper feeding pattern, and preferred upper feeding pattern, reactor inlet is used
Liquid distributor.Unreacted acetone can loop back the first reaction zone by rectification to be continued to react.
In the present invention, by introducing the second segment process, the reaction condition of MIBK synthesis reactor can be significantly relaxed, reduce anti-
Pressure is answered, so as to adjust reaction condition to the scope for being more beneficial for raising MIBK yields.Fully do not convert in first process section
Impurity, is sufficiently reacted in the second segment process, meanwhile, by the guard catalyst in the second segment process, making impurity
Epoxy iso-butane is converted into the yield of isobutanol and reaches 30%~90%, and acetone conversion also can be obtained for the side reaction of isopropanol
Suppress, so as to control the composition and content of reactor outlet impurity, it is to avoid difficult separate substance is refined in downstream and acetone reclaims work
Impurities accumulation is caused finally to affect the normal operation of package unit to reactor with acetone recycle in sequence.
In second process section of the invention, impurity epoxy iso-butane is converted into the yield accessible 100% of isobutanol, but for
Economy consideration, is typically recommended as 60~90%.
In the present invention, the liquid that is synthesized of two-stage process sequentially passes through cut light tower, acetone recovery tower, dehydrating tower, de-
Alcohol tower and MIBK treating columns carry out rectification and purification.Cut light tower is in 5~300KPa of pressure preferably conditions of 100~200KPa
Lower operation；Theoretical cam curve is 5~60, preferably 15~50；Feed entrance point be 10-30 plates, preferred 15-25 plates.Acetone recovery tower
In the conditional operation that pressure is 50~100KPa；Theoretical cam curve is 10~100, preferably 30~60；Feed entrance point is 10~35
Plate, preferably 15~25 plates.Dehydrating tower is 50~500KPa, preferably 100~260KPa in pressure；Theoretical cam curve is 10~60,
It is preferred that 15~50；Feed entrance point be 10~30 plates, preferably 10~25 plates.Dealcoholysis tower pressure be 100~250KPa under the conditions of
Operation；Theoretical cam curve is 15~55；Feed entrance point is 15~25 blocks of plates.MIBK treating columns are 5~200KPa in pressure, preferably
Operate under the conditions of 100~180KPa；Theoretical cam curve 20~60, preferably 30~50；Feed entrance point be 10~40 plates, preferably 15~
20 plates.By being refining to obtain the MIBK products that mass fraction is 99.5%-99.8%.
Two-stage process of the present invention is synthesized liquid after rectification and purification, and the MIBK product purities for obtaining can reach 99.5
~99.8wt%.
The beneficial effects of the present invention is：
1st, two-stage process is adopted, technological parameter is controlled, while realizing that impurity is converted into the isobutanol being easily isolated, and third
Ketone is not hydrogenated to isopropanol as far as possible, extends the service life of MIBK synthetic catalysts, further improves the economic benefit of device.
2nd, in the second segment process guard catalyst introduction, reduce the temperature of MIBK synthesis reactor, improve product
Selectivity.While MIBK products are obtained most of light component is converted into and is easily isolated material in raw material, effective control third
The side reaction of ketone, whole technique is more simple.
3rd, solve the problems, such as the re-using of industrial by-product low-purity acetone, it is to avoid wastage of material, realize by low pure
Degree acetone to the MIBK with high added value is converted.Relative to traditional preparation methods, possess significant cost of material advantage, then match somebody with somebody
The rectification flow of optimization is closed, recoverable acetone and highly purified MIBK products is prepared, makes device possess very strong economic competition
Power.
Description of the drawings
Fig. 1 is the process flow diagram using two reactors
Fig. 2 is using the process flow diagram of two reaction zones
Specific embodiment
The present invention is described in further detail with reference to example below, but the scope of the present invention is not limited to these realities
Apply example.
Gas chromatogram：Shimadzu model GC2010-plus, chromatographic column HP-PONA (50m × 0.2mm × 0.25 μm), injection port
230 DEG C of temperature, heating schedule：40 DEG C, kept for 8 minutes, 10 DEG C/min is warming up to 240 DEG C；Detector temperature is 300 DEG C.
Amberlyst CH-28, wherein DOW Chemical company limited, Pd contents are 0.7wt%；
D5H5A, wherein auspicious section, Pd contents are 5wt%,
The composition of raw materials used by-product low-purity acetone is as shown in table 1 in each embodiment：
The raw material by-product low-purity acetone of table 1 is constituted
| 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 |
| Methanol | 3.09 | 8.25 | 2.41 | 0.75 | 3.09 |
| Acetone | 87.01 | 60 | 95.00 | 78.00 | 87.01 |
| Isopropanol | 0.03 | 0.04 | 0.02 | 0.13 | 0.03 |
| Epoxy iso-butane | 6.30 | 20 | 1.00 | 10.00 | 6.30 |
| The tert-butyl alcohol | 1.59 | 5.89 | 0.64 | 4.36 | 1.59 |
| Iso-butane | 1.20 | 5.29 | 0.68 | 5.22 | 1.20 |
As shown in Figure 1：Raw material, fresh hydrogen and circulating hydrogen enter first reactor, the acetone conversion after reaction
For MIBK；Hydrogen and reacted liquid respectively enter second reactor after reaction, and after second reactor, impurity enters one
Step is converted into isobutanol, and unreacted hydrogen is recycled, and Synthesis liquid enters follow-up rectification flow.
As shown in Figure 2：Raw material, fresh hydrogen and circulating hydrogen sequentially enter the first reaction zone and second reaction zone, real
Existing acetone conversion is that MIBK and epoxy iso-butane are converted into segregative isobutanol.
Embodiment one
The system of non-loading type copper catalyst Cu-1, Cu-2 and Cu-3 in the guard catalyst that the second segment process is used
It is standby：
By Cu (NO3)2·3H2O、Zn(NO3)2·6H2O、Al(NO3)3·9H2O、Ca(NO3)2·4H2O、Mg(NO3)2·
6H2O、Fe(NO3)3·9H2O presses respectively 9:75:40:15:10:2、35:55:25:8:15:1、60:36:26:4:0.61:0.15
Ratio wiring solution-forming 1, solution 2 and solution 3, be slowly added dropwise Na thereto respectively2CO3Aqueous solution, control rate of addition make it
PH is maintained at 4~6, after treating that coprecipitation reaction is completed, aging 12~24h at room temperature；Afterwards vacuum filtration will be precipitated and female
Liquid is separated, and is precipitated with substantial amounts of deionized water rinsing during sucking filtration；Dry 8 at 80~100 DEG C will be deposited in~
12h, then in N2Roasting 4h at atmosphere is lower 400 DEG C；Extrusion molding afterwards, and the method for the catalyst spraying after molding will be contained
The ethanol-water solution for having 1% commercialization KP-853 waterproofing agents is sprayed on catalyst surface, 20~24h of drying at room temperature, you can obtain table
Face scribbles the non-loading type copper catalyst of waterproofing agent.
Wherein Cu mass fractions are that 9% catalyst is denoted as Cu-1 catalyst, and Cu mass fractions are 35% catalyst note
Make Cu-2 catalyst, Cu mass fractions are that 60% catalyst is denoted as Cu-3 catalyst.
Embodiment two
Supported copper catalyst Cu-Sn-1, Cu-Sn-2 and Cu-Sn- in the guard catalyst that second segment process is used
3 preparation：
By CuCl2·2H2O and SnCl4·5H2O is separately added in the stearic acid of melting by certain mass ratio, in 80~
100 DEG C of 6~8h of magnetic agitation, completely rear addition a certain amount of butyl titanate strong agitation 3~5h back covers to be drained off form semi-transparent
Bright colloidal sol, is dried 4~6h, 400 DEG C~500 DEG C 2~4h of roasting in Muffle furnace, afterwards in 350~400 DEG C of hydrogen at 100 DEG C
4~6h is reduced under gas atmosphere.
M (Cu) is finally obtained according to said method:m(Sn):m(TiO2) it is 9:11:80 catalyst Cu-Sn-1, is obtained m
(Cu):m(Sn):m(TiO2) it is 25:5:70 catalyst Cu-Sn-2, is obtained m (Cu):m(Sn):m(TiO2) it is 39:16:45
Catalyst Cu-Sn-3.
Embodiment three
Raw material composition is as shown in table 1, and the catalyst of the first process section is Amberlyst CH-28, and reactor is fixation
Bed reactor, reaction temperature is 100 DEG C, and reaction pressure is 3MPa, and hydrogen-oil ratio (mol ratio) is 0.7, and air speed is 1h-1.Second work
The catalyst of skill section adopts auspicious section D5H5A, and reactor is CSTR, and reaction temperature is 125 DEG C, reaction pressure
For 3MPa, reactor volume is 2L, and catalyst amount is 5g, and the time of staying is 30min.
Gathering the product of the first segment process and the second segment process carries out chromatography, and concrete outcome is listed in table 2.
Reaction result after the two-stage process of table 2
As can be seen from Table 2：During an only segment process, the yield of isobutanol only has 9.84%, and epoxy iso-butane is most of
Conversion is for isobutylaldehyde, and isobutylaldehyde is more difficult with acetone separates, the separation of impact subsequent product.Add second segment reaction process
Afterwards, primary response temperature is in lower temperature, it is also possible to realize that most of epoxy iso-butane is converted into isobutyl by the second segment process
Alcohol, and the selectivity of isobutanol is up to 95.00%, while ensureing the high conversion of acetone and the high selectivity of MIBK, acetone
The yield for being converted into isopropanol is only 0.13%.
The product generated in second segment process is carried out into atmospheric distillation, filler adopts the triangle spiral of Ф 3 × 3, post
High 1m overhead condensations coolant-temperature gage is 25 DEG C, and when tower top temperature is 51 DEG C~53 DEG C, reflux ratio is 5:1, overhead extraction 2-MP, third
The azeotropic mixture of ketone and ethers etc.；When tower top temperature is 57 DEG C~59 DEG C, reflux ratio is 2:1, overhead extraction is acetone, first
The components such as alcohol, isobutylaldehyde；Remaining tower bottoms is carried out into a point liquid, upper oil phase is taken and is continued rectification, be 87 DEG C~107 in tower top temperature
DEG C when, reflux ratio is 5:1, the azeotropic mixture of the azeotropic mixture, isopropanol and isobutanol and MIBK of overhead extraction water and MIBK；Tower top
Temperature is 116~117 DEG C, reflux ratio 5:1, overhead extraction MIBK samples, high purity 99.8wt%.
Example IV
Raw material composition is as shown in table 1, and the catalyst of the first process section is Amberlyst CH-28, and wherein Pd contents are
0.7%, reactor adopts fixed bed reactors, and reaction temperature is 90 DEG C, and reaction pressure is 3MPa, and air speed is 1h-1, hydrogen-oil ratio
(mol ratio) is 0.6.The catalyst of the second process section adopts unsupported Cu-1 catalyst, and reactor is fixed bed reactors,
Reaction temperature is 150 DEG C, and reaction pressure is 0.3MPa, air speed 5h-1, hydrogen-oil ratio (mol ratio) is 0.1.And the first segment process and
Second segment process is carried out respectively in different reactors, and the fed version of this two-stage process is all upper feeding, reactor inlet
With the inert alumina bead that reactor outlet is respectively provided with 40cm.
Gathering the product of the first segment process and the second segment process carries out chromatography, and specific reaction result is listed in
Table 3.
The product generated in second segment process is carried out into atmospheric distillation, filler adopts the triangle spiral of Ф 3 × 3, post
High 1m overhead condensations coolant-temperature gage is 25 DEG C, and when tower top temperature is 51 DEG C~53 DEG C, reflux ratio is 5:1, overhead extraction 2-MP, third
The azeotropic mixture of ketone and ethers etc.；When tower top temperature is 57 DEG C~59 DEG C, reflux ratio is 2:1, overhead extraction is acetone, first
The components such as alcohol, isobutylaldehyde；Remaining tower bottoms is carried out into a point liquid, upper oil phase is taken and is continued rectification, be 87 DEG C~107 in tower top temperature
DEG C when, reflux ratio is 5:1, the azeotropic mixture of the azeotropic mixture, isopropanol and isobutanol and MIBK of overhead extraction water and MIBK；Tower top
Temperature is 116~117 DEG C, reflux ratio 5:1, overhead extraction MIBK samples, high purity 99.8%.
Embodiment five
Raw material composition is as shown in table 1, and using Amberlyst CH-28, wherein Pd contents are the catalyst of the first process section
0.7%, reactor adopts fixed bed reactors, and reaction temperature is 110 DEG C, and reaction pressure is 2MPa, and air speed is 1h-1, hydrogen-oil ratio
(mol ratio) is 0.3.The catalyst of the second process section adopts unsupported Cu-2 catalyst, and reactor is fixed bed reactors,
Reaction temperature is 100 DEG C, and reaction pressure is 2MPa, air speed 1h-1, hydrogen-oil ratio (mol ratio) is 0.3.And the first segment process and
Two step process is carried out in identical reactor, and the fed version of this two-stage process is all upper feeding, reactor inlet, reactor
The inert alumina bead of 20cm is respectively provided between outlet and two-stage process.
Gathering the product of the second segment process carries out chromatography, is as a result listed in table 3.
Embodiment six
Raw material composition is as shown in table 1, the catalyst of the first process section adopt AmberlystCH-28 wherein Pd contents for
0.7%, reactor adopts fixed bed reactors, and reaction temperature is 130 DEG C, and reaction pressure is 2MPa, and air speed is 1.5h-1, hydrogen oil
It is 0.5 than (mol ratio).The catalyst of the second process section adopts unsupported Cu-3 catalyst, and reactor is fixed bed reaction
Device, reaction temperature is 50 DEG C, and reaction pressure is 0.1MPa, air speed 1h-1, hydrogen-oil ratio (mol ratio) is 0.7.And the first segment process
Carry out in the reactor for differing with the second segment process, the fed version of this two-stage process is all lower charging, reactor inlet
With the inert alumina bead that reactor outlet is respectively provided with 40cm.
Gathering the product of the second segment process carries out chromatography, and specific reaction result is listed in table 3.
Reaction result after the two-stage process of table 3
As can be seen from Table 3：Example IV, most of epoxy iso-butane can be realized by the second segment process in five, six
Isobutanol is converted into, and the selectivity of isobutanol is up to respectively 81.11%, 90.00% and 60.00%, while ensureing acetone
High conversion and MIBK high selectivity, acetone conversion is respectively 0.58%, 0.05% and 0.50% for the yield of isopropanol.
Embodiment seven
Raw material is as shown in table 1.The catalyst of the first process section using high-temperature catalyst disclosed in CN201410128345-
3, preparation process refers to technology disclosed in CN200610045641, and reactor adopts fixed bed reactors, and reaction temperature is 110
DEG C, reaction pressure is 3MPa, and air speed is 1.2h-1, hydrogen-oil ratio (mol ratio) is 0.6.The catalyst of the second process section adopts Cu-
Sn-1 catalyst, reactor is fixed bed reactors, and reaction temperature is 50 DEG C, and reaction pressure is 3MPa, air speed 1.2h-1, hydrogen oil
It is 0.6 than (mol ratio).And the first segment process and the second segment process are carried out in the differential responses area of same reactor, charging
Form is upper feeding, and the inert alumina that 20cm is respectively provided between reactor inlet, reactor outlet and two-stage process is little
Ball.Gathering the product of the second segment process carries out chromatography, is as a result listed in table 4.
Embodiment eight
Raw material is as shown in table 1.The catalyst of the first process section using high-temperature catalyst disclosed in CN201410128345-
4, preparation process refers to technology disclosed in CN200610045641, and reactor adopts fixed bed reactors, and reaction temperature is 130
DEG C, reaction pressure is 3MPa, and air speed is 1.2h-1, hydrogen-oil ratio (mol ratio) is 0.6.The catalyst of the second process section adopts Cu-
Sn-2 catalyst, reactor is fixed bed reactors, and reaction temperature is 120 DEG C, and reaction pressure is 3MPa, air speed 2h-1, hydrogen-oil ratio
(mol ratio) is 0.6.And the first segment process and the second segment process are carried out in different reactor, and fed version enters under being all
Material, reactor inlet and reactor outlet are respectively provided with the inert alumina bead of 40cm.Gather the first segment process and second segment
The product of technique carries out chromatography, is as a result listed in table 4.
Embodiment nine
Raw material is as shown in table 1.The catalyst of the first process section adopts Amberlyst CH-28, and wherein Pd contents are
0.7%, reactor adopts fixed bed reactors, and reaction temperature is 110 DEG C, and reaction pressure is 0.1MPa, and air speed is 1.2h-1, hydrogen
Oil is 0.6 than (mol ratio).The catalyst of the second process section adopts Cu-Sn-3 catalyst, and reactor is fixed bed reactors, instead
Temperature is answered for 60 DEG C, reaction pressure is 3MPa, air speed 5h-1, hydrogen-oil ratio (mol ratio) is 0.6.And the first segment process and second
Segment process is carried out in different reactor, and fed version is upper feeding, and reactor inlet and reactor outlet are respectively provided with 40cm
Inert alumina bead.Gathering the product of the first segment process and the second segment process carries out chromatography, is as a result listed in table
4。
Reaction result after the two-stage process of table 4
As can be seen from Table 4：Can realize that most of epoxy iso-butane is converted into isobutanol by the second segment process, and
The selectivity of isobutanol respectively up to 75.00%, 81.00% and 30.00%, while ensureing the high conversion and MIBK of acetone
High selectivity, acetone conversion is respectively 0.23%, 1% and 0.13% for the yield of isopropanol.
Comparative example 1 and comparative example 2
MIBK is synthesized catalyst and ROHM AND HAAS macropore ion exchange life tree is respectively adopted in comparative example 1 and comparative example 2
Fire resistant resin catalyst -3 disclosed in fat Amb-36 and CN201410128345, both load respectively the palladium of 0.7wt% and contain
Amount, boils 24h in 160 DEG C of distillation under pressure water, and the catalyst preparation process of carrying metal palladium is disclosed with reference to CN200610045641
Technology.Reactor inside diameter Ф 20, using multistage heating formula heat-insulation system；Catalyst is the spherical particle of Ф 0.3~1.3, fills out
Loading amount 100ml；By-product acetone mixture and hydrogen cocurrent are through beds.Collection fluid sample analysis, specific reaction
Condition and result are listed in table 5.
The low temperature of table 5 and different catalysts synthesis MIBK contrasts during high temperature
Note：Ethers includes diisopropyl ether, two tertiary butyl ether, methyl isobutylether, methyl tert-butyl ether etc..
Drawn by table 5：Under pyroreaction, epoxy iso-butane can be largely converted into the isobutanol being easily isolated, but
The selectivity relatively low only 78.85% and 69.59% of MIBK.
Claims (17)
1. a kind of method for preparing MIBK by industrial by-product acetone, is carried out with two-stage process：
First segment process, under catalyst action, the acetone conversion in by-product acetone is MIBK, and the epoxy iso-butane in impurity turns
The yield for turning to isobutanol is 1~30%；And
Second segment process, guard catalyst effect under, the epoxy iso-butane in impurity be converted into isobutanol yield be 30~
95%, while acetone conversion is 0.05~1% for the yield of isopropanol；
Guard catalyst described in second segment process is the one kind or many in supported copper catalyst and non-loading type copper catalyst
Kind；
The structure of the supported copper catalyst is Cu-A '/B, and the A ' is one or more in zinc, stannum, lead and bismuth；B is
Amphoteric oxide carrier；
Based on the gross mass of supported copper catalyst, the mass fraction of Cu is 6%~55%；The mass fraction of A ' be 0.01%~
40%；
The structure of the non-loading type copper catalyst be Cu-A-C, wherein A be auxiliary agent, A be Zn and selected from Al, Si, Mg, Fe, Ni,
One or more in Ca, Zr, Ti, Co and K；C is silicone waterproofing agent；
Based on the gross mass of unsupported copper catalyst, the mass fraction of Cu is 5%~65%；The mass fraction of A be 30%~
90%；Based on the gross mass of auxiliary agent A, the mass fraction of Zn is 30~60%；
Hydrogenation reaction temperature is 80~150 DEG C in first segment process；
The reaction temperature of the second segment process is 40~180 DEG C.
2. method according to claim 1, it is characterised in that the first segment process, the epoxy iso-butane in impurity is converted into
The yield of isobutanol is 3~15%；Second segment process, the epoxy iso-butane in impurity be converted into isobutanol yield be 60~
90%.
3. method according to claim 1, it is characterised in that guard catalyst non-loading type copper described in the second segment process
Catalyst.
4. method according to claim 1, it is characterised in that in the structure of the supported copper catalyst A ' be zinc and/
Or stannum；B is one or more in aluminium oxide, beryllium oxide, Zinc Oxide, tin ash, zirconium dioxide and titanium dioxide；The matter of B
Amount fraction is 40%~90%；
The non-loading type copper catalyst, based on the gross mass of unsupported copper catalyst, the mass fraction of C is 0.005%~
10%；Based on the gross mass of auxiliary agent A, it is 0~30% that Al is 0~30%, Si, and remaining is 0~10%；C be alkyl silicic acids salt,
One or more in silanes, silicon resin solution and resin emulsion.
5. method according to claim 4, it is characterised in that B is titanium dioxide in the structure of the supported copper catalyst
Zirconium and/or titanium dioxide；Based on the gross mass of supported copper catalyst, the mass fraction of Cu is 9%~39%；The quality of B point
Number is 45%~80%；
The non-loading type copper catalyst, based on the gross mass of unsupported copper catalyst, the mass fraction of Cu is 9%~60%；A
Mass fraction be 34%~85%；C is alkyl silicic acids salt.
6. method according to claim 5, it is characterised in that B is titanium dioxide in the structure of the supported copper catalyst
Titanium.
7. the method according to any one of claim 1-6, it is characterised in that by-product acetone described in the second segment process
Volume space velocity is 0.5~10h-1。
8. method according to claim 7, it is characterised in that the volume space velocity of by-product acetone is described in the second segment process
1~5h-1。
9. the method according to any one of claim 1-6, it is characterised in that the impurity bag in the industrial by-product acetone
Epoxy iso-butane, methanol, the tert-butyl alcohol, isopropanol, water and t-butyl formate are included, in terms of the gross mass of by-product acetone, wherein, acetone
Content be 60~95wt%, the content of epoxy iso-butane is 1~20wt%.
10. the method according to any one of claim 1-6, it is characterised in that reaction pressure gauge pressure is 0.1~7MPa；
Hydrogen-oil ratio is 0.1~1；The feed volume air speed of by-product acetone is 0.5~2h-1；Wherein, hydrogen-oil ratio refer to hydrogen inlet amount with it is initial
The mol ratio of acetone in by-product acetone.
11. methods according to claim 10, it is characterised in that hydrogenation reaction temperature is 90~130 in the first segment process
℃；Reaction pressure gauge pressure is 0.1~3MPa；Hydrogen-oil ratio is 0.3~0.7；The feed volume air speed of by-product acetone be 0.8~
1.5h-1；Wherein, hydrogen-oil ratio refers to the mol ratio of hydrogen inlet amount and acetone in initial by-product acetone.
12. methods according to any one of claim 1-6, it is characterised in that the reaction pressure gauge pressure of the second segment process
For 0.1~3MPa；Hydrogen-oil ratio is 0.1~1；Wherein, hydrogen-oil ratio refers to hydrogen inlet amount with acetone feed amount in initial by-product acetone
Mol ratio.
13. methods according to claim 12, it is characterised in that the reaction temperature of the second segment process is 50 DEG C~150 DEG C；
Hydrogen-oil ratio is 0.3-0.7；Wherein, hydrogen-oil ratio refers to the mol ratio of hydrogen inlet amount and acetone feed amount in initial by-product acetone.
14. methods according to claim 1, it is characterised in that the catalyst described in the first segment process is multiple for Pd- resins
Close catalyst, Pd-ZSM-5 composite catalysts, Pd/Al2O3Catalyst or Ni/Al2O3Catalyst.
15. methods according to claim 14, it is characterised in that the catalyst described in the first segment process is Pd- resins
Composite catalyst.
16. methods according to any one of claim 1-6, it is characterised in that the first segment process and the second segment process point
Do not carry out in first reactor and second reactor, or respectively in first reaction zone and second reaction zone of same reactor
In carry out；The first reactor and second reactor are identical or different, are separately fixed-bed tube reactor or company
Continuous stirred-tank reactor.
17. methods according to claim 16, it is characterised in that the first reactor is identical with second reactor,
For fixed-bed tube reactor.
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| CN107915612B (en) * | 2016-10-08 | 2020-10-02 | 万华化学集团股份有限公司 | Method for preparing purified MIBK from industrial byproduct waste liquid acetone |
| CN107915615B (en) * | 2016-10-08 | 2020-09-08 | 万华化学集团股份有限公司 | Method for preparing purified MIBK from industrial byproduct waste liquid acetone |
| IT201600106503A1 (en) * | 2016-10-21 | 2018-04-21 | Conser Spa Piazzale Ezio Tarantelli 100 00144 Roma / It | Production process of methyl isobutyl ketone from acetone and related production plant |
| CN109701570B (en) * | 2017-10-26 | 2022-03-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone and preparation method and application thereof |
| CN109701549B (en) * | 2017-10-26 | 2022-03-29 | 中国石油化工股份有限公司 | Catalyst for preparing methyl isobutyl ketone by acetone one-step method and preparation method and application thereof |
| CN109718786B (en) * | 2017-10-30 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB362204A (en) * | 1930-01-07 | 1931-12-03 | Melle Usines Sa | The manufacture of a substitute for amyl alcohol |
| EP0227868A1 (en) * | 1984-09-25 | 1987-07-08 | Sumitomo Chemical Company, Limited | Process for production of methyl isobutyl ketone |
| EP0271182A1 (en) * | 1986-11-08 | 1988-06-15 | Sumitomo Chemical Company, Limited | Alumina catalyst for catalytic production of methyl isobutyl ketone from acetone |
| JP2000229904A (en) * | 1999-02-08 | 2000-08-22 | Mitsui Chemicals Inc | Production of saturated ketone compound |
| CN1331071A (en) * | 2000-06-28 | 2002-01-16 | 中国石油化工集团公司 | Process for synthesizing methylisobutanone from acetone |
| CN102367223A (en) * | 2011-10-18 | 2012-03-07 | 烟台万华聚氨酯股份有限公司 | Synthesis method of isophorone |
| CN102516027A (en) * | 2011-11-14 | 2012-06-27 | 中国海洋石油总公司 | Method for preparing catalyst for coproducing alcohol and ketone according to acetone hydrogenation method |
| CN102806086A (en) * | 2012-08-15 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of catalyst for coproducing isopropanol and methyl isobutyl ketone by acetone hydrogenation |
| CN103936574A (en) * | 2014-04-01 | 2014-07-23 | 万华化学集团股份有限公司 | Method for preparing high-purity methyl isobutyl ketone from industrial by-product acetone waste liquid |
| CN104355975A (en) * | 2014-11-07 | 2015-02-18 | 中国海洋石油总公司 | Method for synthesizing methyl isobutyl ketone from acetone by two-step process |
-
2015
- 2015-10-13 CN CN201510671332.7A patent/CN105237373B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB362204A (en) * | 1930-01-07 | 1931-12-03 | Melle Usines Sa | The manufacture of a substitute for amyl alcohol |
| EP0227868A1 (en) * | 1984-09-25 | 1987-07-08 | Sumitomo Chemical Company, Limited | Process for production of methyl isobutyl ketone |
| EP0271182A1 (en) * | 1986-11-08 | 1988-06-15 | Sumitomo Chemical Company, Limited | Alumina catalyst for catalytic production of methyl isobutyl ketone from acetone |
| JP2000229904A (en) * | 1999-02-08 | 2000-08-22 | Mitsui Chemicals Inc | Production of saturated ketone compound |
| CN1331071A (en) * | 2000-06-28 | 2002-01-16 | 中国石油化工集团公司 | Process for synthesizing methylisobutanone from acetone |
| CN102367223A (en) * | 2011-10-18 | 2012-03-07 | 烟台万华聚氨酯股份有限公司 | Synthesis method of isophorone |
| CN102516027A (en) * | 2011-11-14 | 2012-06-27 | 中国海洋石油总公司 | Method for preparing catalyst for coproducing alcohol and ketone according to acetone hydrogenation method |
| CN102806086A (en) * | 2012-08-15 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of catalyst for coproducing isopropanol and methyl isobutyl ketone by acetone hydrogenation |
| CN103936574A (en) * | 2014-04-01 | 2014-07-23 | 万华化学集团股份有限公司 | Method for preparing high-purity methyl isobutyl ketone from industrial by-product acetone waste liquid |
| CN104355975A (en) * | 2014-11-07 | 2015-02-18 | 中国海洋石油总公司 | Method for synthesizing methyl isobutyl ketone from acetone by two-step process |
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