CN1660751A - Condensation and hydrogenation reaction for preparing carbonyl contained products - Google Patents
Condensation and hydrogenation reaction for preparing carbonyl contained products Download PDFInfo
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- CN1660751A CN1660751A CN 200410103285 CN200410103285A CN1660751A CN 1660751 A CN1660751 A CN 1660751A CN 200410103285 CN200410103285 CN 200410103285 CN 200410103285 A CN200410103285 A CN 200410103285A CN 1660751 A CN1660751 A CN 1660751A
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Abstract
The present invention provides a method for preparing carbonyl contained products which includes the step of making at least one kind of carbonyl contained product condensating and hydrogenating at the situation that hydric and the condensation and hydrogenation catalyst exist,thus to prepare the carbonyl contained products.The characteristics of this method lies in condensation and hydrogenation catalyst including metallic halide strong acid ion exchange resin,this metal is suitable for catalytic hydrogenated reaction.This invention also involving the catalyst defined as above and a method for preparing this catalyst.
Description
Technical field
The present invention relates to prepare the method for carbonyl contained products, be included under the existence of condensation and hydrogenation catalyst and make at least a contain condensation of carbonyl reaction thing and hydrogenation.The invention still further relates to the catalyzer that is used for such method and such Preparation of catalysts.
Background technology
One or more contain the carbonyl reaction thing forming unsaturated carbonyl containing compound to comprise condensation, and the method that the described unsaturated compound of hydrogenation forms saturated carbonyl contained products is known by people.
One of such method is to prepare methyl iso-butyl ketone (MIBK) (MIBK) by acetone.In this method, two acetone molecules condensations obtain diacetone alcohol, and it forms mesityl oxide (MSO) through dehydration, and MSO forms MIBK through hydrogenation.Condensation and dehydration reaction are carried out in the presence of acid catalyst, hydrogenation hydrogenation catalyst for example precious metal in the presence of carry out.
US 3,574, and 763 disclose such method that is prepared MIBK by acetone.But this method is that next step is finished in the existence of single condensation and hydrogenation catalyst.Catalyzer is the form of storng-acid cation exchange resin, and it is doped with precious metal.Described in literary composition, reaction is preferably carried out in 120 to 140 ℃ of temperature ranges.Commercial, such reaction is carried out in 120 to 130 ℃ of temperature usually, and this is owing to catalyzer under comparatively high temps decomposes fast.
DE 4425216 has described the preparation method of storng-acid cation exchange resin, and this resin is based on the cross-linked styrene multipolymer, and this styrol copolymer has the exchange activity sulfonic acid group that links to each other with the polystyrene substrate that contains benzenesulfonyl.The thermostability of such Zeo-karb Yin Qigao is and outstanding, and particularly suitable is made the catalyzer of alkene aquation.But not mentioned condensation reaction.
US 4,269, and 943 have described the method for preparing the storng-acid cation exchange resin that has strengthened thermostability.This method comprises chlorination or bromination storng-acid cation exchange resin and subsequently sulfonation is carried out in chlorination or bromination product.It is said that this catalyzer can be used for pyroreaction, for example alkylation of the aquation of alkene, phenol etc., the temperature of these reactions is higher than 130 ℃.But not mentioned condensation reaction.
EP 1 321 450 discloses the method that is prepared MIBK in the presence of single condensation and hydrogenation catalyst by acetone.In this example, catalyzer is many sulfonation ion-exchange resin catalyst form of doping metals.Prepare MIBK down at 130 ℃, 140 ℃ and 150 ℃.
Also known, in the above-mentioned method for preparing MIBK, formed intermediate MSO can further react with acetone and form a series of oligomeric and high polymeric compounds, and these compounds will produce negative influence to the yield of MIBK.
The unforeseeable result that the inventor obtained shows: when the method that is prepared MIBK by acetone is in high relatively temperature and exists when carrying out under new condensation and the hydrogenation catalyst, follow optionally accepting influence, can improve space-time yield (productivity).This raw catalyst can be resisted decomposition in the following long period of comparatively high temps, and has the mechanical stability of improvement.
Wonderful discovery, the halogenation strong-acid ion exchange resin that wherein comprises the metal (this metal is suitable for catalytic hydrogenation) that is incorporated into wherein provides and has been applicable to the rugged catalyst that is prepared MIBK by acetone.
More surprisingly find, at least in some cases, halogenation of the present invention, metal-adulterated storng-acid cation exchange resin have shown the commercial high mechanical stability of ion exchange resin that can get, the ion exchange resin that these commerce can get comprises single sulfonation ion exchange resin of being used for condensation reaction or many sulfonation ion exchange resin of temperature-stable, and these resins for example are disclosed among the EP1 321 450.
The mechanical stability that improves can obtain proof by the deformability of ion exchange bead reduction, is called as compressibility here.
Summary of the invention
According to an aspect of the present invention, the invention provides a kind of method for preparing carbonyl contained products, be included under the existence of hydrogen and condensation and hydrogenation catalyst and make at least a contain condensation of carbonyl reaction thing and hydrogenation, with the step of preparation carbonyl contained products; The method is characterized in that condensation and hydrogenation catalyst comprise the halogenation strong-acid ion exchange resin that wherein combines metal, this metal is suitable for catalytic hydrogenation.
Preferably only supply with a kind of carbonyl reaction thing that contains.
Contain the carbonyl reaction thing and can comprise aldehydes or ketones, preferably include ketone.In a preferred embodiment of the present invention, this ketone comprises acetone.
The condensation that contains the carbonyl reaction thing can be the dimerization that contains the carbonyl reaction thing.Preferred then to the product after this dimerization product dehydration and the hydrogenation dehydration.
In a preferred embodiment of the present invention, carbonyl contained products comprises the wherein all saturated carbonyl containing compound of all C-Cs.
Preferred carbonyl contained products comprises ketone, the preferred wherein all saturated ketone of all C-Cs.In one embodiment of the invention, ketone can comprise methyl iso-butyl ketone (MIBK) (MIBK).
In a preferred embodiment of the invention, carbonyl contained products contains the carbonyl reaction thing and comprises more carbon atom.Preferred carbonyl contained products has 6 carbon atoms at least.
In a preferred embodiment of the invention, this method is the method that is used for being prepared by acetone MIBK.
Preferred condensation and hydrogenation are carried out in same operation steps.
Catalyzer can comprise the halogenation strong-acid ion exchange resin that combines metal in the resin.This resin preferably includes at least one aromatics part, preferably has the halogen of the aromatic ring keyed jointing of at least one and aromatics part.That is to say that this aromatics partly is halogenated.
Term " aromatics " used in this specification sheets comprises heteroaromatic.
The strongly-acid function of exchange resin can partly be provided by the strongly-acid with resin aromatics part keyed jointing.
Resin can be a sulfonated products, preferably has the sulfonic group of at least one and resin aromatics part keyed jointing.Resin can be many sulfonated products, and each aromatics of one or more aromatics parts of resin partly has the sulfonic group more than.Preferably be less than 20%, partly have sulfonic group more than one more preferably less than each aromatics in 10% the aromatics part.Preferred resin is single sulfonated products, and each aromatics partly has no more than one sulfonic group.
Activity of such catalysts can for: every gram resin is less than 5meqH
+Ion, preferably this value is 3 to 5meq, more preferably 4 to 5meq.
In one embodiment of the invention, catalyzer can comprise through the polystyrene of the copolymerization of halogenation and doping metals and divinylbenzene resin.It is the divinyl benzene crosslinked agent of 2 to 20% (weight parts) and based on sulfonic acidic functionality that these resins have content usually.Preferably in the scope of 0.2 to 6meq/g dried resin, preferred 0.2 to being lower than the 5meq/g dried resin at the volume (capacity) of acidic functionality before halogenation and the doping metals.Before halogenation and mixing, this resin can comprise commercial available strong-acid ion exchange resin, preferred storng-acid cation exchange resin.Will halogenation and adulterated resin can be selected from Amberlyst
TM16, Amberlyst
TM15, Dowex
TMM-31, Lewatit
TMK2431, Purolite
TMCT-175 and Relite
TMCFS/H.
Halogen can comprise any suitable halogen, but preferred Cl or Br.Halogen is Cl preferably.
The halogenation of strong-acid ion exchange resin can be carried out in any suitable mode of working as, and for example with as US4, the similar fashion of describing in 269,943 is carried out, and the document is hereby incorporated by.
Preferred halogenation is carried out in liquid medium, preferred water-bearing media, and preferred temperature is 20 to 30 ℃.The preferred iodine that uses is as catalyzer (for example referring to US 4,269,943, embodiment 3).
Described halogenation (preferred chlorination) also can be carried out in organic medium, for example methylene dichloride and tetracol phenixin.The preferred Lewis acid that uses is as catalyzer.Lewis acid can comprise BF
3, ZnCl
2, AlCl
3Or FeCl
3
Based on dry-matter, the cl content in condensation and the hydrogenation catalyst is preferably 2 to 30 weight %, preferred 5 to 25 weight %, more preferably 15 to 22 weight %.Under the situation of bromo, all wt-% value all doubles.If consider to use other halogen, can be according to providing and the amount of regulating other used halogen based on the identical volumetric molar concentration of the volumetric molar concentration of the chlorine of above-mentioned weight %.
The metal that is incorporated in condensation and the hydrogenation catalyst can comprise following metal: palladium, platinum, iridium, rhodium, ruthenium, osmium, copper, nickel and zirconium preferably comprise precious metal.Preferred precious metal is selected from palladium, ruthenium, rhodium and platinum.Palladium preferably.
The content of preferred precious metal is 0.3 to 2 weight %, more preferably 0.5 to 1.0 weight %.
Metal can be with any suitable mode combination (doping) in condensation and hydrogenation catalyst, for example dipping or coating.Preferably metal is provided in the surface of strong-acid ion exchange resin matrix.
Can be as US 3,574, carrying out like that described in 763 is metal-doped, and the document is hereby incorporated by.
MIBK can synthesize under 130 ℃ that are higher than temperature, preferably is higher than 140 ℃, more preferably is higher than 150 ℃.Expect this method can in addition higher temperature under carry out for example 150 to 170 ℃.Usually, the upper limit of temperature is by the stability decision of catalyzer under comparatively high temps.
Reactor can be typical fixed bed hydrogenation reactor continuously.Pressure can be the 1-100 crust; Preferred 5-60 crust; More preferably 40-50 clings to.Feeding rate (LHSV-liquid hourly space velocity) can be 0.5-10h
-1Preferred 1-8h
-1More preferably 4-7h
-1The mol ratio of hydrogen and ketone can be 0.1-1; Preferred 0.15-0.5; More preferably 0.3-0.4.
According to a further aspect in the invention, the invention provides the catalyzer that is suitable for catalyzing and condensing reaction and hydrogenation, comprise the halogenation strong-acid ion exchange resin that wherein combines metal, this metal is suitable for catalytic hydrogenation.
According to a further aspect in the invention, the invention provides by the carbonyl contained products of method preparation as mentioned above basically.
According to a further aspect in the invention, the invention provides a kind of Preparation of catalysts method that is suitable for catalyzing and condensing reaction and hydrogenation, comprise the steps:
-strong-acid ion exchange resin is provided, and
The described resin of-halogenation also provides metal on resin, this metal is suitable for catalytic hydrogenation.
Preferably, resin provides metal then at first by halogenation on halogenated resin.
Metal can be deposited by ionic species, preferably is deposited on the resin.The preferable alloy ion is reduced into metallic forms, preferably uses hydrogen as reductive agent.
Now the present invention is described by following indefiniteness embodiment:
Fig. 1 is illustrating of laboratory-scale reactors system used among the embodiment 3.
Fig. 2 is compressible the illustrating of being discussed in the illustrative embodiments 4.
Fig. 3 is illustrating of the compressible instrument of measurement used among the embodiment 4.
Embodiment
Embodiment 1: halogenated catalyzer
Being prepared as follows of four kinds of halogenation strongly acidic ion-exchange resin catalysts:
Rise at the 6-that is equipped with agitator, thermometer, chlorine inlet and pressure controller and to place the wet ion-exchange resin catalyst of 2,700 grams in the round bottom glass flask.To the saturated aqueous solution that wherein adds 2.8 liters of iodine.During 16 hours, stir the lasting down 705 gram chlorine that inject.Temperature of reaction must not be higher than 30 ℃ when injecting chlorine.
In case after reaction was finished, washing ion exchange resin was to neutral.
Physical properties according to four kinds of resin catalysts of present method chlorating is listed in the table 1.
Table 1:
| Catalyzer | Solid content (%) | Capacity (meq/g) | Cl content (%) |
| ??Amberlyst 16 | ????50.7 | ????3.67 | ????20.9 |
| ??Purolite CT-175 | ????47.2 | ????3.71 | ????21.3 |
| ??Dowex M-31 | ????52.4 | ????3.53 | ????17.9 |
| ??Relite CFS/H | ????54.2 | ????3.61 | ????21.3 |
Cl content and solid content operating weight % represent.
The catalyst stability of halogenation catalyst
In autoclave, use hot water (160 ℃) to handle ion exchange resin and measure elimination, thereby measure the not stability to hydrolysis of chlorating homologue of the stability to hydrolysis of catalyzer shown in the table 1 and they as the catalytic active center of the function of time.Under 160 ℃ temperature, make ion exchange resin contact with water.Usually, about 10g catalyzer adding is equipped with in the 100ml autoclave of 50ml water, contacts one section specified time down in 160 ℃ then as being provided in the table 2.Strongly-acid capacity with each catalyzer of preset time measuring space.The results are shown in the table 2.
The capacitance loss of discovery chlorination ion exchange resin is stagnated after 240 hours in hydrolysis, and chlorating ion exchange resin has not manifested obviously higher and stable capacitance loss.These results have hinted that chlorination ion exchange resin has obviously longer catalyzer work-ing life.
For example, chlorating Amberlyst not
16 demonstrate the capacitance loss of 0.21meq/g (drying) in during 360 to 600 hours, and chlorating Amberlyst
16 capacitance loss only is 0.05meq/g (drying).
Obviously the capacitance loss that reduces particularly after 240 and 600 hours, shows the stability under the comparatively high temps.
Table 2:
| Catalyzer | Cl content (%) | Capacity 0 hour (meq/g) | Capacity 120 hours (meq/g) | Capacity 240 hours (meq/g) | Capacity 360 hours (meq/g) | Capacity 600 hours (meq/g) |
| ???Amberlyst 16 | ???0 | ????4.83 | ??4.00 | ???3.66 | ??3.44 | ??3.23 |
| ???20.9 | ????3.62 | ??3.20 | ???3.10 | ??3.04 | ??2.99 | |
| ???Purolite CT-175 | ???0 | ????4.81 | ??4.07 | ???3.83 | ??3.58 | ??3.32 |
| ???21.3 | ????3.71 | ??3.35 | ???3.24 | ??3.19 | ??3.13 | |
| ???Dowex M-31 | ???0 | ????4.65 | ??3.35 | ???3.05 | ??2.79 | ??2.51 |
| ???17.9 | ????3.53 | ??3.14 | ???2.83 | ??2.74 | ??2.66 | |
| ???Relite CFS/H | ???0 | ????4.71 | ??3.97 | ???3.73 | ??3.48 | ??3.28 |
| ???21.3 | ????3.61 | ??3.25 | ???3.14 | ??3.09 | ??3.03 |
Cl content is represented with weight percent.
Embodiment 2: melts combine
Palladium is incorporated into and forms aldol condensation and hydrogenation catalyst in the chlorination catalyst.
Flood 50ml chlorating Amberlyst 16 and the chlorating Relite CFS/H for preparing as embodiment 1 respectively with palladium, method is as follows: at first in round-bottomed flask the acetylacetonate palladium is dissolved in the 500ml dehydrated alcohol, and placed ultra sonic bath 15 minutes.The ion exchange resin that adds appropriate amount then, this mixture stay in bathing 45 minutes again.Remove organic solvent through rotary evaporation in vacuo.Use following steps to remove alcohol solvent:
565 millibars, 60 ℃, 1 hour
565 millibars, 70 ℃, 1 hour
565 millibars, 80 ℃, 1 hour
565 millibars, 90 ℃, 1 hour
365 millibars, 90 ℃, 1 hour
165 millibars, 90 ℃, 1 hour
100 millibars, 90 ℃, 1/2 hour
Calcining:
The catalyzer (1.75ml/ minute) of calcining prepared fresh in air.With 2 ℃/minute speed catalyzer is heated to 100 ℃.Under this temperature, kept 3 hours then.
The analysis of the catalyzer of palladium-impregnated:
The results are shown in the table 3 of two kinds of catalyzer:
Table 3:
| Catalyzer | Pd content (weight %) | BET surface-area (m 2/g) | Pore volume (cm 3/g) | Average pore diameter (nm) |
| ??Amberlyst 16 (chlorinations) | ????0 | ???22.98 | ??0.24 | ????41.38 |
| ??Amberlyst 16 (chlorination and doping Pd) | ????0.89 | ???22.23 | ??0.27 | ????49.32 |
| ??Relite CFS/H (chlorination) | ????0 | ???25.91 | ??0.56 | ????86.79 |
| ??Relite CFS/H (chlorination and doping Pd) | ????0.77 | ???23.57 | ??0.34 | ????57.24 |
Pd is expressed as the weight % of dried resin.
Embodiment 3: use the resin catalyst of chlorating, doping palladium, temperature influences the MIBK synthetic.
Present embodiment has used Relite
The CFS/H catalyzer, it is as chlorination among the embodiment 1 and combine palladium therein as embodiment 2.
In the little reactive system of the fixed bed of Fig. 1, carry out the preparation of MIBK.
Charging and product have been analyzed by vapor-phase chromatography and Karl Fischer water titration(method).
The transformation efficiency of acetone, components selection, yield and productivity are as giving a definition
Yield (%)=transformation efficiency * selectivity ... ... ... ... ... ... .. (4)
Catalyst cupport: use Alpha-alumina with 1: 2 volume ratio dilute catalyst (5ml) (1 volume of catalyst: 2 volume aluminum oxide) thus make with reacting relevant heat release and minimize, and catalyst cupport is formed catalytic bed 6 in the fixed-bed micro-reactor 3 of Fig. 1.
The activation of catalyzer: use following method deactivated catalyst in the reactive system of Fig. 1:
● at 0.5h
-1Low liquid hourly space velocity introduce down acetone
● use hydrogen that pressure is increased to 30 crust
● after setting up hydrogen stream, slowly be warming up to 90 ℃
● when the temperature of whole catalyst bed reaches 90 ℃, in hydrogen continues mobile 12 hours, every two hours stop and opening fresh feed pump (to guarantee that catalyst exposure is in reducing in the required enough hydrogen and being unlikely to parch)
● after 12 hours, improve hydrogen flow rate to full process flow rate
● slowly heat up until reaching required bed temperature
MIBK's is synthetic
Synthesizing in the illustrated fixed-bed micro-reactor of Fig. 1 system of MIBK carried out.Acetone feed is introduced in the fixed-bed reactor 3 via charging stock tank 1 by HPLC pump 2.Table 4 has provided feed composition.Hydrogen 4 enters in the reactor 3 by FC5.Reactor 3 loads have aforesaid catalyzer with catalytic bed 6 forms.The internal diameter of reactor 3 is 15mm and is equipped with slip thermopair 7.Before entering reaction zone, the upper half of reactor 3 is used for feeding preheating to required temperature in.By pressure-regulator 8 product in the reactor 3 is transferred in the separating tank 9 then, here product liquid be deposited in the bottom and unreacted hydrogen enters tail gas.Continue to provide hydrogen to compensate the hydrogen that consumes and to keep 30 to 50 pressure that cling to.Use PLC system's controlling reactor (not marking).
Table 4: acetone feed is formed
| Component | Content (weight %) |
| Acetone | ????99.81 |
| Other hydrocarbon | ????0.01 |
| Water | ????0.18 |
Tested the catalyzer Relite of chlorating and dipping Pd according to aforesaid method
CFS/H, condition is that 30 to 50 crust, 120 to 150 ℃, LHSV are 4 to 6h
-1, and the mol ratio of hydrogen and acetone be 0.4 to 0.6.
The results are shown in the table 5 of synthetic method.
Table 5:
| Temperature (℃) | ???121.2 | ????120.9 | ????151.0 | ????151.4 | ????151.8 |
| Pressure (crust) | ???30 | ????30 | ????30 | ????50 | ????30 |
| LHSV(h -1) | ???4.01 | ????6.16 | ????4.01 | ????3.98 | ????6.06 |
| H 2: acetone (mol ratio) | ???0.4 | ????0.6 | ????0.6 | ????0.4 | ????0.4 |
| Acetone conversion (%) | ???32.41 | ????27.62 | ????46.36 | ????49.41 | ????43.80 |
| MIBK yield (%) | ???23.03 | ????14.12 | ????14.77 | ????19.78 | ????21.81 |
| MIBK selectivity (%) | ???88.92 | ????86.58 | ????79.02 | ????82.92 | ????79.15 |
| MIBK productivity (g MIBK/g catalyzer * h) | ???1.563 | ????1.998 | ????1.996 | ????2.209 | ????2.858 |
The invention provides the method that a kind of modification is used to prepare the catalyzer of MIBK, it allows by improving temperature of reaction and by regulating other reaction parameter MIBK synthetic space-time yield being significantly improved.
Temperature is increased to 150 ℃ from 120, productivity increased by 40% (1.998g MIBK/g catalyzer * hour to 2.858g MIBK/g catalyzer * hour).Surprisingly, optionally minimizing only is about 8.5%.
Embodiment 4: the mechanical stability of chlorinated resin
The special characteristic of the mechanical stability of strong-acid ion exchange resin is the deformability of catalyst bead in the fixed bed catalyst filling that is caused by directed flow.This deformability is called as compressibility.
Directed flow can make the ion exchange resin distortion, and the void volume in the catalyst filling can reduce (referring to Fig. 2) like this.
Those skilled in the art know that the minimizing of catalyst filling hollow volume can improve flow velocity, and therefore increase the pressure drop of whole catalyst filling.
Usually, the quadratic power of pressure drop in the reactor and flow velocity is in direct ratio:
dp～w
2
Wherein dp=pressure drop
The w=flow velocity
Mean flow rate in the fixed-bed reactor depends on void volume, and equation is as follows
wk＝w/εk
The mean flow rate in the wk=fixed-bed reactor wherein
ε k=void volume
Void volume ε k in the globular ion exchange resin of filling is about 0.33.The compressibility of 1cm/m described in this embodiment makes void volume ε k reduce by 0.01.
Measure compressibility in the instrument of in as Fig. 3, describing 30.
Bed ion weighting material 31 places round cylinder 32, and this circle cylinder has screening top 33, is full of in the buret 34 of water on stacking it in this screening top then.In check power is applied to fixed bed by moving circle cylinder 35 from following (shown in the arrow 36), thus compression fixed bed 31.
The volume of measuring the water that is occurred on the catalyzer weighting material is measured the amount of this water.The compressibility of ion exchange resin can be determined by following equation:
The common average compressibility of strongly-acid list sulfonated cation exchange resin is 3 to 3.5cm/m.
Storng-acid cation exchange resin is Amberlyst for example
TM36 or Amberlyst
TM38 since its higher sulfonation and more stable to high temperature, its compressibility can increase by 50%, promptly increases to about 4.5cm/m.On the contrary, sulfonation of strongly-acid list and chlorating Zeo-karb are mechanically stables, so that their compressibility is low to moderate 2.4 to 2.7cm/m.
Pd mixes and does not show compressible influence.The compressibility of finding single sulfonation of the present invention, chlorination, the adulterated resin of Pd is 2.4 to 2.7cm/m.
According to the present invention,, the influence of pressure drop has been reduced about 15% with respect to many sulfonation catalysts.
The results are compiled in the table 6,
Wherein
-used as among the embodiment 1 preparation the chlorizate with character as shown in table 1.
-used as the chlorination with character as shown in table 3 of preparation among the embodiment 2 and the product of doping Pd.
Table 6
| Catalyzer | Compressibility [cm/m] | Void volume ε k | Influence (1/ ε k) to pressure drop 2 |
| Ball packing | ????0 | ???0.33 | ????9.18 |
| Single sulfonated products | |||
| Amberlyst 16 | ????3.1 | ???0.299 | ????11.18 |
| Dowex M-31 | ????3.5 | ???0.295 | ????11.49 |
| Purolite CT-175 | ????3.3 | ???0.297 | ????11.34 |
| Relite CFS/H | ????3.4 | ???0.296 | ????11.41 |
| Many sulfonated products | |||
| Amberlyst 36 | ????4.5 | ???0.285 | ????12.31 |
| Amberlyst 38 | ????4.7 | ???0.283 | ????12.49 |
| Single sulfonation and chlorating product | |||
| Chlorination Amberlyst 16 | ????2.4 | ???0.306 | ????10.67 |
| Chlorination Dowex M-31 | ????2.7 | ???0.303 | ????10.89 |
| Chlorination Purolite CT-175 | ????2.8 | ???0.302 | ????10.96 |
| Chlorination Relite CFS/H | ????2.7 | ???0.303 | ????10.89 |
| The product of single sulfonation, chlorination, doping Pd | |||
| The Amberlyst of chlorination and doping Pd 16 | ????2.4 | ???0.306 | ????10.67 |
| The Relite of chlorination and doping Pd CFS/H | ????2.7 | ???0.303 | ????10.89 |
Claims (25)
1. the method for preparing carbonyl contained products is included in hydrogen and condensation and hydrogenation catalyst and exists down, makes at least a carbonyl reaction thing that contains carry out condensation and hydrogenation, with the step of preparation carbonyl contained products; The method is characterized in that condensation and hydrogenation catalyst comprise the halogenation strong-acid ion exchange resin that wherein combines metal, this metal is suitable for catalytic hydrogenation.
2. the process of claim 1 wherein a kind of form of ketone only is provided contain the carbonyl reaction thing.
3. the method for claim 2, wherein ketone is acetone.
4. claim 2 or 3 each methods, the condensation that wherein contains the carbonyl reaction thing comprises the dimerization that contains the carbonyl reaction thing, and makes the dehydration of dimerization product then, and the product after the hydrogenation dehydration.
5. the method for aforementioned each claim, wherein carbonyl contained products comprises ketone, and this ketone ratio contains the carbonyl reaction thing and contains more carbon atom.
6. the method for claim 5, wherein carbonyl contained products has 6 carbon atoms at least.
7. the method for claim 6, wherein carbonyl contained products is a methyl iso-butyl ketone (MIBK).
8. the method for aforementioned each claim wherein prepares methyl iso-butyl ketone (MIBK) by acetone.
9. the method for aforementioned each claim, wherein condensation and hydrogenation are carried out in same operation steps.
10. the method for aforementioned each claim, wherein the halogenation strong-acid ion exchange resin comprises at least one aromatics part, has the halogen of the aromatic ring keyed jointing of at least one and aromatics part.
11. the method for claim 10, wherein resin is a sulfonated products, has the sulfonic group of at least one and resin aromatics part keyed jointing.
12. the method for claim 11 wherein is less than each aromatics in 10% the aromatics part and partly has sulfonic group more than one.
13. the method for claim 12, wherein resin is that each aromatics partly has no more than one sulfonic single sulfonated products.
14. the method for aforementioned each claim, wherein resin catalyst comprises polystyrene and the divinylbenzene resin through the copolymerization of halogenation and doping metals.
15. the method for aforementioned each claim, wherein the halogen of halogenation strong-acid ion exchange resin is selected from Cl and Br.
16. the method for claim 15, wherein halogen is Cl.
17. the method for claim 16, wherein the cl content in condensation and hydrogenation catalyst is 2 to 30 weight %.
18. the method for aforementioned each claim, the metal that wherein is incorporated in condensation and the hydrogenation catalyst is a precious metal, is selected from palladium, ruthenium, rhodium and platinum.
19. the method for claim 18, wherein metal is a palladium.
20. claim 18 or 19 each methods, wherein the content of precious metal is 0.3 to 2 weight %.
21. the method for aforementioned each claim, it is to carry out being higher than under 130 ℃ the temperature.
22. a catalyzer that is applicable to catalyzing and condensing reaction and hydrogenation comprises the halogenation strong-acid ion exchange resin that wherein is combined with metal, this metal is suitable for catalytic hydrogenation.
23. one kind by each the carbonyl contained products of method preparation of claim 1 to 21.
24. a method for preparing the catalyzer that is suitable for catalyzing and condensing reaction and hydrogenation comprises the steps:
-strong-acid ion exchange resin is provided, and
The described resin of-halogenation also provides metal on resin, this metal is suitable for catalytic hydrogenation.
25. the method for claim 24, wherein resin provides metal then at first by halogenation on halogenated resin.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102343282A (en) * | 2010-06-30 | 2012-02-08 | 罗门哈斯公司 | Multireaction bifunctional polymeric catalyst |
| CN106944134A (en) * | 2017-04-14 | 2017-07-14 | 丹东明珠特种树脂有限公司 | The synthetically prepared use resin catalyst of ethylene glycol tertbutyl ether and its method of modifying |
| CN115974699A (en) * | 2022-12-25 | 2023-04-18 | 江苏湘园化工有限公司 | Preparation method of aromatic diamine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269943A (en) * | 1979-08-23 | 1981-05-26 | Rohm And Haas Company | Thermally stable resins prepared by bromination or chlorination of aromatic polymer beads followed by sulphonation |
| US6977314B2 (en) * | 2001-12-19 | 2005-12-20 | Rohm And Haas Company | Metal-doped sulfonated ion exchange resin catalysts |
-
2004
- 2004-11-16 CN CNB2004101032858A patent/CN100427447C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102343282A (en) * | 2010-06-30 | 2012-02-08 | 罗门哈斯公司 | Multireaction bifunctional polymeric catalyst |
| US8492594B2 (en) | 2010-06-30 | 2013-07-23 | Rohm And Haas Company | Multireaction bifunctional polymeric catalyst |
| CN106944134A (en) * | 2017-04-14 | 2017-07-14 | 丹东明珠特种树脂有限公司 | The synthetically prepared use resin catalyst of ethylene glycol tertbutyl ether and its method of modifying |
| CN115974699A (en) * | 2022-12-25 | 2023-04-18 | 江苏湘园化工有限公司 | Preparation method of aromatic diamine |
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| CN100427447C (en) | 2008-10-22 |
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