CN104437455A - Ester-exchange-reaction catalyst, as well as preparation method and application thereof - Google Patents
Ester-exchange-reaction catalyst, as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104437455A CN104437455A CN201410576696.2A CN201410576696A CN104437455A CN 104437455 A CN104437455 A CN 104437455A CN 201410576696 A CN201410576696 A CN 201410576696A CN 104437455 A CN104437455 A CN 104437455A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- ester exchange
- calcium
- molding adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 *C(C(*)O1)OC1=O Chemical compound *C(C(*)O1)OC1=O 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses an ester-exchange-reaction catalyst, as well as a preparation method and an application thereof. The catalyst comprises a catalytic active ingredient containing potassium oxide-calcium oxide composite oxide and a porous oxide forming binder with the specific surface area being between 50m<2>/g and 230m<2>/g, wherein the mass ratio of potassium oxide to calcium oxide to the forming binder is between (0.05-0.25) to 1.0 to (0.2-0.8). The preparation method comprises the following steps: (1) uniformly dispersing a potassium oxide precursor, a calcium oxide precursor and forming binder powder in water with the mass ratio of potassium element to calcium element to the forming binder being (0.06-0.3) to 1.0 to (0.3-1.12); (2) adding auxiliary agents, uniformly mixing, drying and grinding; (3) adding a forming additive, forming and drying; and (4) roasting for 3-8 hours. The catalyst disclosed by the invention is high in catalytic activity, good in anti-inactivation property, simple in preparation and low in cost and can be applied in synthesis of polyalcohol carbonate ester.
Description
Technical field
The invention belongs to new catalyst field, particularly, relate to a kind of catalyst for ester exchange reaction, its preparation method and application, more specifically, relate to and a kind ofly synthesize the catalyst of polyalcohol carbonic ester, its preparation method and application by polyalcohol and dialkyl carbonate through ester exchange reaction.
Background technology
Ester exchange reaction refers to that ester and alcohol generate the reaction of another kind of ester and another kind of alcohol under acidity or base catalyst catalysis.Ester exchange reaction is industrially widely used, and such as, biodiesel is exactly the aliphatic acid mono alkyl ester obtained through ester exchange reaction by animal and plant fat and methyl alcohol or ethanol, and most typical is fatty acid methyl ester.The key that ester-exchange reaction efficiently carries out is selecting of catalyst for ester exchange reaction.Along with the sharp increase day by day of yield of biodiesel, new and effective catalyst for ester exchange reaction development attracts wide attention.On the other hand, the industrialization of biodiesel creates a large amount of by-product glycerins.It is reported, often produce 1.0kg biodiesel, by by-product 0.1kg glycerine.Therefore, realize the Efficient Conversion of glycerine, to promote Biodiesel sustainable development, seem more urgent.Now having developed multiple transformation of glycerol technology, be wherein glycerol carbonate by transformation of glycerol is one of focus of research.Glycerol carbonate is a kind of important industrial chemicals, of many uses, wide market.Be that the method for Material synthesis glycerol carbonate is mainly divided into carbon dioxide process, carbon monoxide method, urea method and ester-interchange method etc. with glycerine.At present, being hopeful most to realize industrialized route is ester-interchange method, especially with the method that glycerine and dimethyl carbonate are Material synthesis glycerol carbonate, there is reaction condition gentleness, glycerol conversion yield is high, environmental friendliness, product is easy to the advantages such as separation, is one of prefered method of suitability for industrialized production glycerol carbonate.
Catalyst at present for ester exchange reaction mainly comprises liquid acid or base catalyst, solid acid or base catalyst and lipase etc.Relative to enzyme catalyst and liquid catalyst, solid catalyst, particularly solid base catalyst, have technique simple, environmental pollution is little, is easy to the advantages such as recycling, is more promising catalyst for ester exchange reaction type.Wherein calcium oxide belongs to conventional solid base catalyst, because its raw material sources are wide, low price, environmental friendliness and catalytic activity are higher and obtain more application.The system thinkings such as the Ochoa-Gomez J.R. catalytic performance of Cao Catalyst glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, found that, under good condition, the conversion ratio of glycerine can reach about 95% (J.R.Ochoa-G ó mez, O.G ó mez-Jim é nez-Aberasturi, B.Maestro-Madurga, et al.Appl.Catal.A:Gen.366 (2009) 315 – 324.).But they also find that calcium oxide catalyst is to reuse in process inactivation obvious, is unfavorable for the large-scale application of this catalyst.Inventor developed a kind of calcium oxide-based preformed catalyst, form (P.F.Lu, H.J.Wang, K.K.Hu.Chem.Eng.J.228 (2013) 147 – 154.) by calcium oxide and the alumina composite taking calcium carbonate as presoma.The catalyst that the method obtains is 80 DEG C in reaction temperature, and dimethyl carbonate and glycerine mol ratio are 3:1, and catalyst (in calcium oxide) and glycerine mol ratio are 0.15:1.0, and reaction time 5h, can obtain the glycerol conversion yield of 95%.But this catalyst activity or on the low side, reaches the reaction time needed for higher glycerol conversion yield long; Meanwhile, this catalyst resistance to deactivation can be also good not, and when the 5th is reused, glycerol conversion yield is less than 65%.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of catalyst for ester exchange reaction, its preparation method and application, its object is to by by potassium oxide-calcium oxide composite oxides and molding adhesive compound, maintain catalyst activity, solve existing catalyst for ester exchange reaction activity thus on the low side, the technical problem that resistance to deactivation is not good.
For achieving the above object, according to one aspect of the present invention, provide a kind of catalyst for ester exchange reaction, described catalyst comprises catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, described molding adhesive is porous oxide, and its specific area is at 50m
2/ g to 230m
2between/g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is in (0.05 ~ 0.25): 1.0:(0.2 ~ 0.8) between.
Preferably, described catalyst for ester exchange reaction, molding adhesive described in it is kaolin, aluminium oxide or diatomite.
According to another aspect of the present invention, provide a kind of preparation method of catalyst for ester exchange reaction, comprise the following steps:
(1) using potassium oxide precursor, calcium oxide precursor powder and molding adhesive powder as raw material, raw material is dispersed in water, make the mass ratio of wherein potassium element, calcium constituent and molding adhesive in (0.06 ~ 0.3): 1.0:(0.3 ~ 1.12), obtain raw material mixed liquor;
(2) in the raw material mixed liquor in step (1), add assistant agent, drying and grinding after Homogeneous phase mixing, obtains powders A; Described assistant agent comprises expanding agent, and expanding agent accounts for 2% to 5% of material quality;
(3) in the powders A obtained in step (2), shaping assistant is added, extruded and dry, obtain catalyst precarsor;
(4) catalyst precarsor will obtained in step (3), at 500 DEG C at 900 DEG C, roasting 3 is little of 8 hours, namely obtains described catalyst for ester exchange reaction.
Preferably, described preparation method, potassium oxide precursor described in it is potassium hydroxide, potash or potassium nitrate; Described calcium oxide precursor is calcium hydroxide, calcium carbonate or calcium acetate; Described molding adhesive is kaolin, aluminium oxide or diatomite.
Preferably, described preparation method, its step (2) described expanding agent is polyacrylamide, active carbon or polyethylene glycol, is preferably polyacrylamide.
Preferably, described preparation method, the shaping assistant described in its step (3) is the Ludox of mass concentration between 20% to 30%.
Preferably, described preparation method, described in its step (2), assistant agent also comprises extrusion aid, and extrusion aid accounts for 2% to 5% of material quality, and described extrusion aid is preferably sesbania powder.
According to another aspect of the present invention, provide a kind of described catalyst for ester exchange reaction and be applied to synthesis polyalcohol carbonic ester, described polyalcohol carbonic ester meets the structure of formula (I)
Wherein, R
1represent that hydrogen atom or carbon atom quantity are the straight chain of 1 ~ 9 or the alkyl containing side chain; R
2represent that carbon atom quantity is the straight chain of 1 ~ 9 or the alkyl containing side chain.
Preferably, described catalyst for ester exchange reaction is applied to synthesis polyalcohol carbonic ester, and polyalcohol carbonic ester described in it is glycerol carbonate.
Preferably, described catalyst for ester exchange reaction is applied to synthesis polyalcohol carbonic ester, its catalytic temperature is between 65 DEG C ~ 85 DEG C, reaction raw materials is dimethyl carbonate and glycerine, its mol ratio is between 1:1 to 5:1, in catalyst, calcium oxide and glycerine mol ratio are between 0.05:1 to 0.2:1, and catalysis time 1 is little of 5 hours.
In general, the above technical scheme conceived by the present invention compared with prior art, can obtain following beneficial effect:
(1) catalytic activity is high, repeatedly reusable.Preformed catalyst provided by the invention has very high activity to glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and catalyst is when without calcination processing, reuses after 10 times, still can obtain the glycerol conversion yield of more than 80%.
(2) raw material sources are wide, with low cost, are easy to preparation.The presoma of the active component of catalyst of the present invention is potassium nitrate and calcium carbonate, and the two raw material sources is wide, low price.What the preparation process of catalyst related generally to several material is uniformly mixed operation, fairly simple.
(3) not pollute the environment and equipment.The main component of catalyst of the present invention is potassium, the oxide of calcium or salt, environmentally friendly, and does not also almost corrode equipment.
(4) mechanical strength is high, and bed pressure drop is little.Catalyst of the present invention has fixing shape, has higher mechanical strength, and to form beds little compared with the pressure drop of fine catalyst, be applicable to the requirement of industrial reactor.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the catalyst for ester exchange reaction obtained by embodiment 1;
Fig. 2 is the XRD spectra of the catalyst for ester exchange reaction obtained by embodiment 10;
Fig. 3 is the XRD spectra of catalyst for ester exchange reaction obtained by embodiment 11.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Catalyst for ester exchange reaction provided by the invention, comprises catalytic active component and molding adhesive, and described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is at 50m
2/ g to 230m
2between/g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is in (0.05 ~ 0.25): 1.0:(0.2 ~ 0.8) between.Described molding adhesive is preferably kaolin, aluminium oxide or diatomite, and wherein aluminium oxide is commonly used as activated alumina.
Catalyst for ester exchange reaction provided by the invention, its preparation method, comprises the following steps:
(1) using potassium oxide precursor, calcium oxide precursor powder and molding adhesive powder as raw material, raw material is dispersed in water, make the mass ratio of wherein potassium element, calcium constituent and molding adhesive in (0.06 ~ 0.3): 1.0:(0.3 ~ 1.12), obtain raw material mixed liquor; Described potassium oxide precursor is potassium hydroxide, potash or potassium nitrate, preferred potassium nitrate; Described calcium oxide precursor is calcium hydroxide, calcium carbonate or calcium acetate, preferred calcium carbonate; Described molding adhesive is kaolin, aluminium oxide or diatomite, preferential oxidation aluminium, conventional activated alumina.
(2) in the raw material mixed liquor in step (1), add assistant agent, drying and grinding after Homogeneous phase mixing, obtains powders A; Described assistant agent comprises expanding agent, and expanding agent accounts for 2% to 5% of material quality; Described expanding agent is polyacrylamide, active carbon or polyethylene glycol, is preferably polyacrylamide.Time dry, temperature is no more than 200 DEG C.
Preferably, described assistant agent also comprises extrusion aid, and extrusion aid accounts for 2% to 5% of material quality, and described extrusion aid is preferably sesbania powder.
(3) in the powders A obtained in step (2), shaping assistant is added, extruded and dry, obtain catalyst precarsor; Described shaping assistant is the Ludox of mass concentration between 20% to 30%.Time dry, temperature is no more than 200 DEG C.
Preferably, by the powders A obtained in step (2), extruded moulding in former, and be cut into
short cylindrical shape solid.
(4) catalyst precarsor will obtained in step (3), at 500 DEG C at 900 DEG C, roasting 3 is little of 8 hours, namely obtains described catalyst for ester exchange reaction.
Catalyst for ester exchange reaction provided by the invention, be applied to synthesis polyalcohol carbonic ester, described polyalcohol carbonic ester meets the structure of formula (I)
Wherein, R
1represent that hydrogen atom or carbon atom quantity are the straight chain of 1 ~ 9 or the alkyl containing side chain; R
2represent that carbon atom quantity is the straight chain of 1 ~ 9 or the alkyl containing side chain.This polyalcohol carbonic ester is obtained through ester exchange reaction by polyalcohol and dialkyl carbonate.
Described polyalcohol meets the structure of formula (II)
Wherein, R
1represent that hydrogen atom or carbon atom quantity are the straight chain of 1 ~ 9 or the alkyl containing side chain; R
2represent that carbon atom quantity is the straight chain of 1 ~ 9 or the alkyl containing side chain.Preferably, described polyalcohol is glycerine.
Described dialkyl carbonate meets the structure of formula (III)
Wherein, R
3and R
4can be the same or different, represent that carbon atom quantity is the straight chain of 1 ~ 9 or the alkyl containing side chain respectively.Preferably, described dialkyl carbonate is dimethyl carbonate.
Preferably, catalyst for ester exchange reaction provided by the invention, be applied to synthesis of glycerol carbonate, catalytic temperature is between 65 DEG C ~ 85 DEG C, reaction raw materials is dimethyl carbonate and glycerine, its mol ratio is between 1:1 to 5:1, and in described catalyst, calcium oxide and glycerine mol ratio are between 0.05:1 to 0.2:1, and catalysis time 1 is little of 5 hours.Described glycerol carbonate structure is such as formula shown in (IV)
Be below embodiment:
Embodiment 1
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is activated alumina.
Through characterizing, the mechanical strength of gained catalyst is 60N/cm.As shown in Figure 1, the main component of XRD analysis display catalyst is calcium oxide, has no obvious potassium oxide and alumina species characteristic peak in XRD spectra.XRD spectra mesosilicic acid calcium species is because the silicon dioxde reaction in calcium oxide and shaping assistant Ludox produces.
Described catalyst for ester exchange reaction, its preparation method, comprises the following steps:
(1) using potassium oxide precursor, calcium oxide precursor powder and molding adhesive powder as raw material, be dispersed in by raw material in water, the mass ratio making wherein potassium element, calcium constituent and molding adhesive is 0.17:1.0:0.84, obtains raw material mixed liquor; Described potassium oxide precursor is potassium nitrate; Described calcium oxide precursor is calcium carbonate; Described molding adhesive is activated alumina.
(2) in the raw material mixed liquor in step (1), add assistant agent, drying and grinding after Homogeneous phase mixing, obtains powders A; Described assistant agent comprises expanding agent, and expanding agent accounts for 3% of material quality; Described expanding agent is polyacrylamide.Time dry, temperature is 100 DEG C.
Described assistant agent also comprises extrusion aid, and extrusion aid accounts for 3% of material quality, and described extrusion aid is sesbania powder.
(3) add shaping assistant in the powders A obtained in step (2), extruded moulding in former, is cut into
short cylindrical shape solid, and dry, obtain catalyst precarsor; Described shaping assistant to be mass concentration be 24% Ludox.Time dry, temperature 100 DEG C.
(4) catalyst precarsor will obtained in step (3), at 800 DEG C, roasting 5 hours, namely obtains described catalyst for ester exchange reaction.
Described catalyst for ester exchange reaction, is applied to synthesis of glycerol carbonate, catalytic temperature 80 DEG C, reaction raw materials is dimethyl carbonate and glycerine, its mol ratio is 3:1, and used catalyst and glycerine mol ratio are 0.1:1 (in calcium oxide), catalysis time 2 hours.
After reaction terminates, take out product, with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 98.54%, and glycerol carbonate yield is 84.96%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 15 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 90.52%, and glycerol carbonate yield is 86.47%; After using for 10th time, glycerol conversion yield is 82.56%, and glycerol carbonate yield is 77.51%; After using for 15th time, glycerol conversion yield is 75.27%, and glycerol carbonate yield is 71.81%.
Embodiment 2
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but the precursor changing potassium oxide is potash.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 99.01%, and glycerol carbonate yield is 87.02%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 77.51%, and glycerol carbonate yield is 73.50%.
Embodiment 3
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but the precursor changing potassium oxide is potassium hydroxide.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 92.30%, and glycerol carbonate yield is 86.15%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 67.18%, and glycerol carbonate yield is 63.65%.
Embodiment 4
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but the precursor changing calcium oxide is calcium acetate.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 93.63%, and glycerol carbonate yield is 82.02%.
Embodiment 5
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but the precursor changing calcium oxide is calcium hydroxide.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 88.57%, and glycerol carbonate yield is 79.39%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 64.17%, and glycerol carbonate yield is 62.08%.
Embodiment 6
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.05:1.0:0.3.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but changes the consumption of potassium nitrate and aluminium oxide, makes the mass ratio of wherein potassium element, calcium constituent and molding adhesive be 0.06:1.0:0.42.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and can obtain glycerol conversion yield is 93.60%, and glycerol carbonate yield is 85.0%.
Embodiment 7
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.25:1.0:0.6.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but changes the consumption of potassium nitrate, makes the mass ratio of wherein potassium element, calcium constituent and molding adhesive be 0.28:1.0:0.84.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 99.27%, and glycerol carbonate yield is 89.64%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 78.45%, and glycerol carbonate yield is 74.94%.
Embodiment 8
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.2.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but changes the consumption of activated alumina, makes the mass ratio of wherein potassium element, calcium constituent and molding adhesive be 0.17:1.0:0.3.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 99.29%, and glycerol carbonate yield is 85.42%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 91.34%, and glycerol carbonate yield is 85.68%.
Embodiment 9
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.8.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but changes the consumption of activated alumina, makes the mass ratio of wherein potassium element, calcium constituent and molding adhesive be 0.17:1.0:1.12.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 99.24%, and glycerol carbonate yield is 90.71%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 76.28%, and glycerol carbonate yield is 73.48%.
Embodiment 10
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is activated alumina.
Through characterizing, the mechanical strength of gained catalyst is 44N/cm.As shown in Figure 2, the main component of XRD analysis display catalyst is calcium oxide, has no obvious potassium oxide and alumina species characteristic peak in XRD spectra.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but change sintering temperature is 700 DEG C.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 96.02%, and glycerol carbonate yield is 85.29%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 65.96%, and glycerol carbonate yield is 63.30%.
Embodiment 11
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is activated alumina.
Through characterizing, the mechanical strength of gained catalyst is 38N/cm.As shown in Figure 3, the main component of XRD analysis display catalyst is calcium oxide, has no obvious potassium oxide and alumina species characteristic peak in XRD spectra.XRD spectra mesosilicic acid calcium species is because the silicon dioxde reaction in calcium oxide and shaping assistant Ludox produces.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 1, but change sintering temperature is 900 DEG C.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 1, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 99.33%, and glycerol carbonate yield is 89.82%.Be directly used in after reclaiming catalyst 50mL methanol wash 3 times and react next time.According to above condition, catalyst is reused 5 times, and form with gas chromatographic analysis product, after can obtaining the 5th reaction, glycerol conversion yield is 75.71%, and glycerol carbonate yield is 73.91%.
Embodiment 12
Catalyst for ester exchange reaction prepared by embodiment 1 is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, reaction condition is identical with embodiment 1, but change reaction temperature is 75 DEG C.With gas chromatographic analysis product composition, can obtain glycerol conversion yield is 88.12%, and glycerol carbonate yield is 83.18%.
Embodiment 13
Catalyst for ester exchange reaction prepared by embodiment 1 is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, reaction condition is identical with embodiment 1, but change reaction temperature is 85 DEG C.With gas chromatographic analysis product composition, can obtain glycerol conversion yield is 99.30%, and glycerol carbonate yield is 86.56%.
Embodiment 14
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 150m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is kaolin.
Described catalyst for ester exchange reaction, its preparation method, comprises the following steps:
(1) using potassium oxide precursor, calcium oxide precursor powder and molding adhesive powder as raw material, be dispersed in by raw material in water, the mass ratio making wherein potassium element, calcium constituent and molding adhesive is 0.17:1.0:0.84, obtains raw material mixed liquor; Described potassium oxide precursor is potassium nitrate; Described calcium oxide precursor is calcium carbonate; Described molding adhesive is kaolin.
(2) in the raw material mixed liquor in step (1), add assistant agent, drying and grinding after Homogeneous phase mixing, obtains powders A; Described assistant agent comprises expanding agent, and expanding agent accounts for 2% of material quality; Described expanding agent is polyethylene glycol.Time dry, temperature is 100 DEG C.
Described assistant agent also comprises extrusion aid, and extrusion aid accounts for 2% of material quality, and described extrusion aid is sesbania powder.
(3) add shaping assistant, extruded moulding in former in the powders A obtained in step (2), and be cut into
short cylindrical shape solid, and dry, obtain catalyst precarsor; Described shaping assistant to be mass concentration be 24% Ludox.Time dry, temperature is 100 DEG C.
(4) catalyst precarsor will obtained in step (3), at 800 DEG C, roasting 3 hours, namely obtains described catalyst for ester exchange reaction.
Described catalyst for ester exchange reaction, is applied to synthesis of glycerol carbonate, and catalytic temperature is at 65 DEG C, and reaction raw materials is dimethyl carbonate and glycerine, and its mol ratio is 1:1, and in described catalyst, calcium oxide and glycerine mol ratio are 0.05:1, catalysis time 5 hours.After reaction terminates, take out product, with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 71.13%, and glycerol carbonate yield is 62.90%.
Embodiment 15
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 50m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.15:1.0:0.6.Described molding adhesive is diatomite.
Described catalyst for ester exchange reaction, its preparation method, comprises the following steps:
(1) using potassium oxide precursor, calcium oxide precursor powder and molding adhesive powder as raw material, be dispersed in by raw material in water, the mass ratio making wherein potassium element, calcium constituent and molding adhesive is 0.17:1.0:0.84, obtains raw material mixed liquor; Described potassium oxide precursor is potassium nitrate; Described calcium oxide precursor is calcium carbonate; Described molding adhesive is diatomite.
(2) in the raw material mixed liquor in step (1), add assistant agent, drying and grinding after Homogeneous phase mixing, obtains powders A; Described assistant agent comprises expanding agent, and expanding agent accounts for 5% of material quality; Described expanding agent is active carbon.Time dry, temperature is 100 DEG C.
Described assistant agent also comprises extrusion aid, and extrusion aid accounts for 5% of material quality, and described extrusion aid is sesbania powder.
(3) add shaping assistant, extruded moulding in former in the powders A obtained in step (2), and be cut into
short cylindrical shape solid, and dry, obtain catalyst precarsor; Described shaping assistant to be mass concentration be 24% Ludox.Time dry, temperature is 100 DEG C.
(4) catalyst precarsor will obtained in step (3), at 800 DEG C, roasting 8 hours, namely obtains described catalyst for ester exchange reaction.
Described catalyst for ester exchange reaction, is applied to synthesis of glycerol carbonate, and catalytic temperature is at 70 DEG C, and reaction raw materials is dimethyl carbonate and glycerine, and its mol ratio is 5:1, and in described catalyst, calcium oxide and glycerine mol ratio are 0.2:1, catalysis time 1 hour.After reaction terminates, take out product, with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 73.46%, and glycerol carbonate yield is 71.43%.
Embodiment 16
A kind of catalyst for ester exchange reaction, comprise catalytic active component and molding adhesive, described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is 230m
2/ g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is 0.05:1.0:0.6.Described molding adhesive is activated alumina.
Described catalyst for ester exchange reaction, its preparation method is identical with embodiment 5, but changes the consumption of potassium nitrate and aluminium oxide, and the mass ratio making wherein potassium element, calcium constituent and molding adhesive is 0.06:1.0:0.84, and to change sintering temperature be 500 DEG C.Obtained catalyst is used for glycerine and dimethyl carbonate ester exchange synthesis of glycerol carbonate, and reaction condition is identical with embodiment 5, and with gas chromatographic analysis product composition, can obtain glycerol conversion yield is 85.14%, and glycerol carbonate yield is 78.31%.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a catalyst for ester exchange reaction, is characterized in that, comprises catalytic active component and molding adhesive, and described catalytic active component is potassium oxide-calcium oxide composite oxides, and described molding adhesive is porous oxide, and its specific area is at 50m
2/ g to 230m
2between/g, wherein the mass ratio of potassium oxide, calcium oxide and molding adhesive is in (0.05 ~ 0.25): 1.0:(0.2 ~ 0.8) between.
2. catalyst for ester exchange reaction as claimed in claim 1, it is characterized in that, described molding adhesive is kaolin, aluminium oxide or diatomite.
3. the preparation method of catalyst for ester exchange reaction as claimed in claim 1 or 2, is characterized in that, comprise the following steps:
(1) using potassium oxide precursor, calcium oxide precursor powder and molding adhesive powder as raw material, raw material is dispersed in water, make the mass ratio of wherein potassium element, calcium constituent and molding adhesive in (0.06 ~ 0.3): 1.0:(0.3 ~ 1.12) between, obtain raw material mixed liquor;
(2) in the raw material mixed liquor in step (1), add assistant agent, drying and grinding after Homogeneous phase mixing, obtains powders A; Described assistant agent comprises expanding agent, and expanding agent accounts for 2% to 5% of material quality;
(3) in the powders A obtained in step (2), shaping assistant is added, extruded and dry, obtain catalyst precarsor;
(4) catalyst precarsor will obtained in step (3), at 500 DEG C at 900 DEG C, roasting 3 is little of 8 hours, namely obtains described catalyst for ester exchange reaction.
4. preparation method as claimed in claim 3, it is characterized in that, described potassium oxide precursor is potassium hydroxide, potash or potassium nitrate; Described calcium oxide precursor is calcium hydroxide, calcium carbonate or calcium acetate; Described molding adhesive is kaolin, aluminium oxide or diatomite.
5. preparation method as claimed in claim 3, it is characterized in that, step (2) described expanding agent is polyacrylamide, active carbon or polyethylene glycol, is preferably polyacrylamide.
6. the preparation method as described in claim 3 to 5 any one, is characterized in that, described in step (2), assistant agent also comprises extrusion aid, and extrusion aid accounts for 2% to 5% of material quality, and described extrusion aid is preferably sesbania powder.
7. catalyst for ester exchange reaction as claimed in claim 1 or 2, be applied to synthesis polyalcohol carbonic ester, described polyalcohol carbonic ester meets the structure of formula (I)
Wherein, R
1represent that hydrogen atom or carbon atom quantity are the straight chain of 1 ~ 9 or the alkyl containing side chain; R
2represent that carbon atom quantity is the straight chain of 1 ~ 9 or the alkyl containing side chain.
8. catalyst for ester exchange reaction is applied to synthesis of glycerol carbonate as claimed in claim 7, it is characterized in that, described polyalcohol carbonic ester is glycerol carbonate.
9. catalyst for ester exchange reaction is applied to synthesis of glycerol carbonate as claimed in claim 8, it is characterized in that, catalytic temperature is between 65 DEG C ~ 85 DEG C, reaction raw materials is dimethyl carbonate and glycerine, its mol ratio is between 1:1 to 5:1, in catalyst as claimed in claim 1 or 2, calcium oxide and glycerine mol ratio are between 0.05:1 to 0.2:1, and catalysis time 1 is little of 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410576696.2A CN104437455A (en) | 2014-10-24 | 2014-10-24 | Ester-exchange-reaction catalyst, as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410576696.2A CN104437455A (en) | 2014-10-24 | 2014-10-24 | Ester-exchange-reaction catalyst, as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104437455A true CN104437455A (en) | 2015-03-25 |
Family
ID=52884664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410576696.2A Pending CN104437455A (en) | 2014-10-24 | 2014-10-24 | Ester-exchange-reaction catalyst, as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437455A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941622A (en) * | 2015-05-26 | 2015-09-30 | 上海应用技术学院 | Catalyst used in biodiesel preparation process and preparation method for catalyst |
| CN105435768A (en) * | 2015-11-10 | 2016-03-30 | 北京石油化工学院 | Process method for synthesizing propylene carbonate by urea alcoholysis |
| CN105709785A (en) * | 2014-12-05 | 2016-06-29 | 临沂中通科技有限公司 | Catalyst for preparing glycerol carbonate, using method and application thereof |
| KR101793530B1 (en) | 2016-01-14 | 2017-11-06 | 울산대학교 산학협력단 | Catalyst for producing glycerol carbonate from glycerol and carbon dioxide and preparation method of the same |
| CN113769770A (en) * | 2020-06-09 | 2021-12-10 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate through ester exchange, catalyst and application |
| CN113786830A (en) * | 2021-08-24 | 2021-12-14 | 万华化学(四川)有限公司 | Preparation method and application of catalyst for treating acetylene device carbon black hydrolysis and acetylene hydrocarbon-containing waste gas absorption |
| CN113908877A (en) * | 2021-11-15 | 2022-01-11 | 浙江工业大学 | Dolomite-nitrate/chloride composite catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3526623A (en) * | 1965-12-17 | 1970-09-01 | Marathon Oil Co | Urethane drying oils |
| CN101822992A (en) * | 2010-05-26 | 2010-09-08 | 华中科技大学 | Catalyst for synthesis of glycerol carbonate and preparation method thereof |
| CN101939284A (en) * | 2008-02-11 | 2011-01-05 | 催化蒸馏技术公司 | Process for continuous production of organic carbonates or organic carbamates and solid catalysts therefore |
| CN103524476A (en) * | 2013-10-16 | 2014-01-22 | 广西科学院 | Method for synthesizing co-produced glycerol carbonate and short-carbon-chain carbonate by using multi-element reaction system |
-
2014
- 2014-10-24 CN CN201410576696.2A patent/CN104437455A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3526623A (en) * | 1965-12-17 | 1970-09-01 | Marathon Oil Co | Urethane drying oils |
| CN101939284A (en) * | 2008-02-11 | 2011-01-05 | 催化蒸馏技术公司 | Process for continuous production of organic carbonates or organic carbamates and solid catalysts therefore |
| CN101822992A (en) * | 2010-05-26 | 2010-09-08 | 华中科技大学 | Catalyst for synthesis of glycerol carbonate and preparation method thereof |
| CN103524476A (en) * | 2013-10-16 | 2014-01-22 | 广西科学院 | Method for synthesizing co-produced glycerol carbonate and short-carbon-chain carbonate by using multi-element reaction system |
Non-Patent Citations (4)
| Title |
|---|
| JIANWEI ZHANG ET AL.: "Preparation of KOH/CaO/C Supported Biodiesel Catalyst and Application Process", 《SCIENTIFIC RESEARCH》, vol. 2, 31 August 2014 (2014-08-31) * |
| PENGFEI LU ET AL.: "Synthesis of glycerol carbonate from glycerol and dimethyl carbonate over the extruded CaO-based catalyst", 《CHEMICAL ENGINEERING JOURNAL》, vol. 228, 7 May 2013 (2013-05-07) * |
| 杨玲梅等: "ＫＯＨ负载的不同催化剂催化合成生物柴油", 《化工进展》, vol. 31, 31 December 2012 (2012-12-31) * |
| 王华军等: "成型催化剂 K2O/CaO/Al2O3 催化甘油与碳酸二甲酯酯交换合成甘油碳酸酯", 《中国化学会第29届学术年会摘要集-第12分会：催化化学》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709785A (en) * | 2014-12-05 | 2016-06-29 | 临沂中通科技有限公司 | Catalyst for preparing glycerol carbonate, using method and application thereof |
| CN105709785B (en) * | 2014-12-05 | 2018-10-09 | 临沂中通科技有限公司 | A kind of catalyst being used to prepare carbonic acid glyceride, its application method and its application |
| CN104941622A (en) * | 2015-05-26 | 2015-09-30 | 上海应用技术学院 | Catalyst used in biodiesel preparation process and preparation method for catalyst |
| CN105435768A (en) * | 2015-11-10 | 2016-03-30 | 北京石油化工学院 | Process method for synthesizing propylene carbonate by urea alcoholysis |
| CN105435768B (en) * | 2015-11-10 | 2017-10-31 | 北京石油化工学院 | The process of alcoholysis of urea for synthesizing propylene carbonate and the preparation method of catalyst |
| KR101793530B1 (en) | 2016-01-14 | 2017-11-06 | 울산대학교 산학협력단 | Catalyst for producing glycerol carbonate from glycerol and carbon dioxide and preparation method of the same |
| CN113769770A (en) * | 2020-06-09 | 2021-12-10 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate through ester exchange, catalyst and application |
| CN113769770B (en) * | 2020-06-09 | 2024-04-02 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate by transesterification, catalyst and application |
| CN113786830A (en) * | 2021-08-24 | 2021-12-14 | 万华化学(四川)有限公司 | Preparation method and application of catalyst for treating acetylene device carbon black hydrolysis and acetylene hydrocarbon-containing waste gas absorption |
| CN113786830B (en) * | 2021-08-24 | 2023-08-15 | 万华化学(四川)有限公司 | Preparation method and application of catalyst for treating acetylene device carbon black water desorption alkyne-containing waste gas |
| CN113908877A (en) * | 2021-11-15 | 2022-01-11 | 浙江工业大学 | Dolomite-nitrate/chloride composite catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104437455A (en) | Ester-exchange-reaction catalyst, as well as preparation method and application thereof | |
| Algoufi et al. | Synthesis of glycerol carbonate by transesterification of glycerol with dimethyl carbonate over K-zeolite derived from coal fly ash | |
| CN104722305B (en) | One kind is applied to multi component mixed gas catalst for synthesis of methanol and its preparation method and application | |
| Zhang et al. | Mesoporous Al–Mo oxides as an effective and stable catalyst for the synthesis of biodiesel from the esterification of free-fatty acids in non-edible oils | |
| CN107285995B (en) | Method for preparing methanol by using carbon dioxide and hydrogen | |
| US9409847B2 (en) | Catalyst for single step conversion of glycerol to acrylic acid and process for the preparation thereof | |
| JP2012136516A (en) | Process for producing olefin | |
| CN104475109A (en) | Catalyst for preparing sec-butyl alcohol and preparation method of catalyst | |
| CN105728018A (en) | ZSM-5 zeolite catalyst for alkylation of benzene and methanol, preparation method and application thereof | |
| CN104785261A (en) | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof | |
| CN103551149B (en) | Method for fast preparing dimethyl ether steam reforming hydrogen production catalyst by virtue of alternate microwave | |
| CN104646049A (en) | Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas | |
| MY188850A (en) | Solid catalyst for manufacturing fatty acid methyl or ethyl ester and method for manufacturing fatty acid methyl or ethyl ester using the same | |
| CN114160119A (en) | Dolomite-molybdenum trioxide composite catalyst for preparing acrolein through glycerol dehydration and preparation method thereof | |
| CN102527426A (en) | Preparation method for catalyst for preparing ethylene by dehydrating ethanol | |
| CN102698752B (en) | Copper-aluminum catalyst for hydrogen production by methanol reforming, and preparation method and application thereof | |
| Aresta et al. | Large scale utilization of carbon dioxide: from its reaction with energy rich chemicals to (Co)-processing with water to afford energy rich products. Opportunities and barriers | |
| CN103242149B (en) | Method for selectively preparing acraldehyde and hydroxy-acetone | |
| CN103450004A (en) | Environment-friendly high-efficiency method for synthesizing adipic acid by catalytically oxidating adipic dialdehyde | |
| CN107417494A (en) | The method that a kind of aliphatic acid original position hydrogenation prepares fatty alcohol | |
| CN101380576B (en) | Catalyst for hydrogenolysis of rare glycerol to produce diatomic alcohol and preparation method thereof | |
| TWI648394B (en) | Method for producing biodiesel and triacetin | |
| KR101431328B1 (en) | Preparation method of ethanol through synthesis gas using a ferrieirite catalyst | |
| CN104549409A (en) | Preparation method of compound porous molecular sieve catalyst | |
| US20200231523A1 (en) | Method for directly producing ethanol from syngas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150325 |