CN103965045A - Preparation process and device for glycerol triacetate - Google Patents
Preparation process and device for glycerol triacetate Download PDFInfo
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- CN103965045A CN103965045A CN201410187628.7A CN201410187628A CN103965045A CN 103965045 A CN103965045 A CN 103965045A CN 201410187628 A CN201410187628 A CN 201410187628A CN 103965045 A CN103965045 A CN 103965045A
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- glycerine
- glycerine triacetate
- dehydration
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- hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a continuous production technology and production device for producing environmental-friendly and non-toxic glycerol triacetate by catalyzing polyacid intercalated hydrotalcite. The current process of industrially producing the glycerol triacetate by mainly taking sulfuric acid, phosphoric acid and other inorganic liquid acid as catalysts through a batch still has the defects of environment pollution, unsafe production, low production efficiency and the like. According to the preparation process and device disclosed by the invention, green and high-efficiency polyacid intercalated catalysts are selected to replace the sulfuric acid and the phosphoric acid and a fixed bed process is selected for continuous production. The preparation method has the advantages of high catalytic activity as well as favorable selectivity, recycling property and environment friendliness; the production efficiency is greatly increased and the discharge of three wastes is reduced; a solid foundation is laid for green production of the glycerol triacetate and further industrial production practice application.
Description
Technical field
The present invention relates to a kind of preparation method of ester class, especially a kind of preparation technology of glycerine triacetate and device.
Background technology
Glycerine triacetate, claims again vanay, English glyceryl triacetate by name; Triacetate, is a kind of performance safety, to the friendly type innoxious solvent of human body.Its structural formula is as follows:
Glycerine triacetate dissolves in alcohol, ether, benzene, chloroform and Viscotrol C, can dissolve soluble cotton, cellulose acetate, acroleic acid resin, polyvinyl acetate (PVA) etc.Its physicochemical property are in table 1.1.
The physics of table 1.1 glycerine triacetate, chemical property
Glycerine triacetate can be used as nontoxic type softening agent, be easy to biological degradation, the alternative original poisonous plasticizer DOP in some fields, for PVC material, PLA material, PVAc emulsion, reach the effect of DOP, be widely used in the industries such as food, food product pack, toy for children and nursing materials, makeup, estimated along with the restriction of country to phthalic ester plasticizer, its demand can significantly be promoted year by year, has popularizing application prospect widely
At present, the most frequently used synthetic technology of glycerine triacetate is to adopt glycerine and Glacial acetic acid as raw material, using the vitriol oil, phosphoric acid as catalyzer, under the existence with aqua, in batch reactor, reacts, and produces glycerine triacetate.In batch still, react, because the reaction that generates intermediate product is carried out with reacting in same still of final product of production, can cause speed of reaction to reduce, and due to not fully reaction of raw material, in dehydration, a large amount of acetic acid can be followed entrainer and be removed together with water, and this can reduce the yield of product, increases the discharge of material cost and the three wastes.Adopt acidic liquid acid as catalyzer simultaneously, can cause corrosion to equipment, reaction finishes rear catalyst neutralisation and can cause again brine waste, weighting ring environment pollution, and there is the shortcomings such as constant product quality is poor.
In Chinese patent application CN102115444A, disclose a kind of serialization and produced technique and the device of glycerine triacetate; comprise the steps: that glycerine, acetic acid, band aqua, acidic liquid catalysts are sent into reactor after mixing carries out esterification at 140 DEG C～170 DEG C, then carries out esterification products acidylate, refining.Its shortcoming is to have adopted liquid acid, and strong to equipment corrosion, environmental pollution is large.
Along with the development of catalytic science and the reinforcement of environmental consciousness, high, the environment amenable catalyzer of How to choose catalytic activity, employing serialization, the production technique that level of automation is high become an industrial large research topic of synthetic glycerine triacetate.
Summary of the invention
The present invention is applied to the hydrotalcite of a class polyacid intercalation as catalyzer and produces in glycerine triacetate reaction; and adopt fixed bed form to realize the continuous production device of glycerine triacetate; by this preparation method; to improve the production efficiency of glycerine triacetate; stabilised quality, reduces the three wastes, protection of the environment.
Technical scheme disclosed by the invention is: a kind of preparation technology of glycerine triacetate, comprises the following steps:
A) glycerine, acetic acid and band aqua are pre-mixed, preheating, then add the fixed-bed reactor that are loaded with the hydrotalcite catalyst of polyacid intercalation or the houghite of polyacid intercalation to carry out esterification;
B) above-mentioned esterification reaction product is sent into dehydration tower and carry out distillation dehydration, tower top temperature is 80 DEG C ~ 100 DEG C;
C) material after above-mentioned dehydration is sent into acidylate still, and add acylating agent to carry out acidylate, then the refining glycerine triacetate product that obtains.
The molecular composition of the hydrotalcite described in the present invention is Mg
6al
2(OH)
16cO
34H
2o, it is a kind of anion type laminated compound.Mg in hydrotalcite
2+, A1
3+by M
2+, M
3+isomorphous substitution obtains a compounds of structural similitude, is called houghite, general molecular formula: M
2+1-XM
3+x (OH)
2(A
n-) X/nyH
2o, wherein M
2+=Mg
2+, Ni
2+, Co
2+, Zn
2+, Cu
2+deng; M
3+=Al
3+, Cr
3+, Fe
3+, Sc
3+deng; A
n-for negatively charged ion that can stable existence in basic solution, as: C0
3 2-, NO
3 -, Cl
-, OH
-, S0
4 2-deng; X=0.2～0.33, y=0～6.Different M
2+and M
3+, different interstitial anion A
-, just can form different houghites.
Preferably, described hydrotalcite is the hydrotalcite that directly prepares undried; Divalent metal in the laminate of described hydrotalcite is Mg
2+, trivalent metal cation is Al
3+, interlayer anion is NO
3 -.
Preferably, the chemical formula of the negatively charged ion of described polyacid is [XM
11coO
39]
n-, wherein X=P or Si; M=W or Mo; N is valence number, n=5-6.Preferably, can adopt the magnesium aluminum-hydrotalcite of nitrate radical intercalation in the present invention, the chemical formula of the magnesium aluminum-hydrotalcite of described nitrate radical intercalation is [Mg
6al
2(OH)
16] (XM
11coO
39)
2/nyH
2o; Wherein n=5-6, X=P or Si, M=W or Mo, y=3-6.
Preferably, the mass ratio of described glycerine and acetic acid is 1:2.5 ~ 1:3.5.
Preferably, be describedly selected from the one in ethyl acetate, benzene, toluene with aqua, the described consumption with aqua accounts for glycerine, acetic acid and with 5% ~ 10% of aqua total mass.
Preferably, described acylating agent is aceticanhydride, and the consumption of described aceticanhydride is the c) 3%-8% of the quality of the material after dewatering of above-mentioned steps.
Preferably, the condition of described acylation reaction is 160 ~ 180 DEG C of acidylate temperature, and the time is 1 ~ 2h.
Preferably, described esterification reaction temperature is 120 DEG C ~ 140 DEG C.
Preferably, described esterification reaction pressure is 0.20MPa ~ 0.40MPa.
Preferably, the reaction time of esterification in described fixed-bed reactor is 20 ~ 30h.
Because the method described in the present invention is that continuous processing is prepared glycerine triacetate, therefore require catalyst catalytic performance stable, can adapt to the production that output is larger, catalyzer 260 Kg described in the present invention can be used in the catalytic production of 1000 tons of glycerine triacetates, and the polyacid intercalation hydrotalcite catalyzer that only need to account for product quality 0.026% just can complete esterification.While feeding intake in method described in the present invention, general glycerine drops in material-compound tank with the speed of 280-350 Kg/h, acetic acid 950-1100 Kg/h, band aqua 70-140 Kg/h.
Preferably, in the preparation technology of glycerine triacetate described in the present invention, be: glycerine, acetic acid and band aqua are pre-mixed, by the first preheater by secondary flash vapors by heating material to 110 DEG C ~ 120 DEG C, then through the second preheater by heating material to 125 DEG C ~ 135 DEG C; Then, the material after preheating enters the fixed-bed reactor that are loaded with polyacid intercalation hydrotalcite catalyzer and carries out esterification 130 DEG C ~ 135 DEG C left and right; Esterification reaction pressure is 0.25MPa ~ 0.35MPa, and the residence time of esterification in described fixed-bed reactor is 20 ~ 30h; Above-mentioned esterification reaction product is pumped into dehydration tower and carry out distillation dehydration, preferred, tower top temperature is 85 DEG C ~ 90 DEG C; Material after dehydration tower dehydration is sent into acidylate still, add aceticanhydride to carry out acidylate, then refine and obtain glycerine triacetate product.
According to the present invention, acetic acid, glycerine and band aqua are pre-mixed, be preferably in material-compound tank and mix, blending means is not particularly limited.In the present invention, catalyzer is to be contained on fixed-bed reactor, esterification is carried out to catalysis, and this catalytic way had both been brought into play the catalytic activity that polyacid system is good, kept and realized the heterogenize of catalyzer, esterification is carried out in the confinement space of hydrotalcite, improved the selectivity of reaction; Make again catalyzed reaction can be applicable to serialization production requirement, greatly reduce energy consumption level.
In order better to carry out esterification, described mixture enters and preferably carries out preheating before reactor, the present invention to preheating without any restriction, can one-level preheating, also can multistage preheating.The present invention preferably carries out two-stage preheating, first mixture is sent into the first preheater, uses secondary flash-off steam to be heated 100 DEG C-130 DEG C, is preferably 110 DEG C-120 DEG C; Described secondary flash-off steam is the recycling of the steam condenses to other techniques, and object is save energy, and the present invention originates without any restriction to it.Mixture after preheating is sent into the second preheater, be heated to 125 DEG C-135 DEG C, thermal source is live steam, and live steam described herein is the steam of temperature well known to those skilled in the art more than 150 DEG C.
The outlet of the fixed-bed reactor for esterification described in the present invention is connected with the import of dehydration tower.The invention also discloses a kind of device for the preparation of glycerine triacetate, this device comprises fixed-bed reactor and dehydration tower, and the discharge end of described fixed-bed reactor is connected with the feed end of described dehydration tower; Described device also comprises bypass channel and acidylate still, and described bypass channel connects the dehydrated mouth of described dehydration tower, and described acidylate still connects the discharge port of described dehydration tower.
In order to improve the utilising efficiency with aqua, the present invention preferably will be with aqua to recycle, and the described recovery method with aqua disclosed by the invention is as follows: the azeotrope with aqua and water steams from dehydration column overhead, enters layering groove after condensation.In layering groove, condensed azeotrope is divided into organic phase and water, and lower floor's water is drawn, and upper organic phase is band aqua, is back in dehydration tower and continues to use.Layering groove can use layering groove well known to those skilled in the art, and the present invention is not particularly limited.
The present invention is not particularly limited acidylate still, process for refining and operating parameters thereof, is preferably equipment well-known to those skilled in the art and technological operation.
The present invention preferably adopts dcs well-known to those skilled in the art (DCS control techniques) to control whole production technique, can realize whole system closed-loop operation, each reference mark is all with bound warning with from conditioning function, be provided with multiple teletransmission alarms in tank field and production scene simultaneously, can realize safe and intelligent control, reduce the harm of production technique to people, and reduced human cost.
By the way, the invention discloses a kind of serialization production technology and device that utilizes polyacid intercalation hydrotalcite catalytic production environment-protecting asepsis type glycerine triacetate.At present industrial production glycerine triacetate mainly adopts the acid of the inorganic liquid such as sulfuric acid, phosphoric acid as catalyzer, adopts batch still to produce, and this technique mainly exists many-sided problems such as environmental pollution, safety in production, production efficiency be low.The present invention has selected a class green, polyacid intercalation catalyzer substitutes sulfuric acid and phosphoric acid efficiently, select fixed-bed process to carry out serialization production, not only have that catalytic activity is high, selectivity good, reusing is good, and environmental friendliness, greatly promote production efficiency, reduce the discharge of the three wastes, for greenization production and the further Industrialized Production Practice application of glycerine triacetate are laid a good foundation.Compared with prior art, technical solution of the present invention has the following advantages:
1, compared with preparing the acid catalyst vitriol oil or phosphoric acid in glycerine triacetate with traditional continuous processing, adopt the polyacid intercalation hydrotalcite catalyzer of supramolecular structure, can make temperature of reaction greatly reduce, reactive behavior is good, and transformation efficiency is high, and selectivity is good.
2, new catalyst is very little to the corrodibility of equipment, and good stability in continuous processing equipment is easy and simple to handle, and recyclable recycling does not need to neutralize remaining catalyzer, has reduced wastewater flow rate, and environmental pollution is little.
3, continuous device has been realized the control of DCS system, has improved greatly production efficiency.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of glycerine triacetate provided by the invention is described.
brief description of the drawings
Fig. 1 is preparation technology's schema of glycerine triacetate.
Embodiment
[embodiment 1]
Glycerine, acetic acid, band aqua are heated to 125 DEG C ~ 135 DEG C, then material is dropped into material-compound tank with the speed of glycerine 300 Kg/h, acetic acid 1000 Kg/h, band aqua 100 Kg/h, the fixed-bed reactor of squeezing into continuously the magnesium aluminum-hydrotalcite catalyzer of the nitrate radical intercalation that is mounted with 200 Kg after mixing through recycle pump, carry out esterification; Fixed-bed reactor control temperature is between 130 DEG C ~ 135 DEG C, and pressure-controlling is at 0.28MPa; The residence time of material in fixed-bed reactor is controlled at 24h; material after esterification enters dehydration tower and carries out distillation dehydration; controlling dehydration column overhead temperature is 86 DEG C; in the time that tower top does not have moisture content to distillate; material after dehydration is sent into acidylate still 160 DEG C ~ 180 DEG C acylation reactions; time is controlled at 1 ~ 2h, carries out the process for refining such as depickling, dehydration after acidylate completes again, and finally obtains glycerine triacetate finished product.In the present embodiment, the chemical formula of the magnesium aluminum-hydrotalcite catalyzer of described nitrate radical intercalation is [Mg
6al
2(OH)
16] (PW
11coO
39)
2/53H
2o.
According to proportioning raw materials, theory obtains glycerine triacetate 710 Kg/h, the actual finished product 696Kg h that obtains, and yield is 98%.
[embodiment 2]
By glycerine, acetic acid, band aqua by 2 pipeline heatings to 125 DEG C ~ 135 DEG C, then material is dropped into material-compound tank with glycerine 300KG/h, acetic acid 1000KG/h, speed with aqua 100KG/h, the fixed-bed reactor of squeezing into continuously the magnesium aluminum-hydrotalcite catalyzer that is mounted with nitrate radical intercalation after mixing through recycle pump, carry out esterification; Fixed-bed reactor control temperature is between 120 DEG C ~ 130 DEG C, and pressure-controlling is at 0.20MPa; The residence time of material in fixed-bed reactor is controlled at 20h; material after esterification enters dehydration tower and carries out distillation dehydration; controlling dehydration column overhead temperature is 80 DEG C; in the time that tower top does not have moisture content to distillate; material after dehydration is sent into acidylate still and carry out acidylate operation; after acidylate completes, carry out again the process for refining such as depickling, dehydration, finally obtain glycerine triacetate finished product.In the present embodiment, the chemical formula of the magnesium aluminum-hydrotalcite catalyzer of described nitrate radical intercalation is [Mg
6al
2(OH)
16] (SiW
11coO
39)
2/53H
2o.
According to proportioning raw materials, theory obtains glycerine triacetate 710KG/h, the actual finished product 696KG/h that obtains, and yield is 98%.
[embodiment 3]
By glycerine, acetic acid, band aqua by 2 pipeline heatings to 125 DEG C ~ 135 DEG C, then material is dropped into material-compound tank with glycerine 300KG/h, acetic acid 900KG/h, speed with aqua 100KG/h, the fixed-bed reactor of squeezing into continuously the hydrotalcite catalyst that is mounted with polyacid intercalation after mixing through recycle pump, carry out esterification; Fixed-bed reactor control temperature is between 120 DEG C ~ 130 DEG C, and pressure-controlling is at 0.20MPa; The residence time of material in fixed-bed reactor is controlled at 20h; material after esterification enters dehydration tower and carries out distillation dehydration; controlling dehydration column overhead temperature is 80 DEG C; in the time that tower top does not have moisture content to distillate; material after dehydration is sent into acidylate still and carry out acidylate operation; after acidylate completes, carry out again the process for refining such as depickling, dehydration, finally obtain glycerine triacetate finished product.In the present embodiment, the chemical formula of the hydrotalcite catalyst of described polyacid intercalation is [Mg
6al
2(OH)
16] (SiMo
11coO
39)
36H
2o.
According to proportioning raw materials, theory obtains glycerine triacetate 710KG/h, the actual finished product 682KG/h that obtains, and yield is 96%.
[embodiment 4]
By glycerine, acetic acid, band aqua by 2 pipeline heatings to 125 DEG C ~ 135 DEG C, then material is dropped into material-compound tank with glycerine 350KG/h, acetic acid 1050KG/h, speed with aqua 130KG/h, the fixed-bed reactor of squeezing into continuously the hydrotalcite catalyst that is mounted with polyacid intercalation after mixing through recycle pump, carry out esterification; Fixed-bed reactor control temperature is between 120 DEG C ~ 130 DEG C, and pressure-controlling is at 0.20MPa; The residence time of material in fixed-bed reactor is controlled at 20h; material after esterification enters dehydration tower and carries out distillation dehydration; controlling dehydration column overhead temperature is 80 DEG C; in the time that tower top does not have moisture content to distillate; material after dehydration is sent into acidylate still and carry out acidylate operation; after acidylate completes, carry out again the process for refining such as depickling, dehydration, finally obtain glycerine triacetate finished product.In the present embodiment, the chemical formula of the hydrotalcite catalyst of described polyacid intercalation is [Mg
6al
2(OH)
16] (SiW
11coO
39)
35H
2o.
According to proportioning raw materials, theory obtains glycerine triacetate 829KG/h, the actual finished product 804KG/h that obtains, and yield is 97%.
[embodiment 5]
By glycerine, acetic acid, band aqua by 2 pipeline heatings to 125 DEG C ~ 135 DEG C, then material is dropped into material-compound tank with glycerine 350KG/h, acetic acid 1120KG/h, speed with aqua 130KG/h, the fixed-bed reactor of squeezing into continuously the hydrotalcite catalyst that is mounted with polyacid intercalation after mixing through recycle pump, carry out esterification; Fixed-bed reactor control temperature is between 120 DEG C ~ 130 DEG C, and pressure-controlling is at 0.20MPa; The residence time of material in fixed-bed reactor is controlled at 20h; material after esterification enters dehydration tower and carries out distillation dehydration; controlling dehydration column overhead temperature is 80 DEG C; in the time that tower top does not have moisture content to distillate; material after dehydration is sent into acidylate still and carry out acidylate operation; after acidylate completes, carry out again the process for refining such as depickling, dehydration, finally obtain glycerine triacetate finished product.In the present embodiment, the chemical formula of the hydrotalcite catalyst of described polyacid intercalation is [Mg
6al
2(OH)
16] (P Mo
11coO
39)
34H
2o.
According to proportioning raw materials, theory obtains glycerine triacetate 829KG/h, the actual finished product 813KG/h that obtains, and yield is 98%.
[embodiment 6]
Glycerine, acetic acid and band aqua are pre-mixed, by the first preheater with secondary flash-off steam by heating material to 110 DEG C ~ 120 DEG C, then through the second preheater by heating material to 125 DEG C ~ 135 DEG C; Then the material after preheating is dropped into material-compound tank with glycerine 280KG/h, acetic acid 784KG/h, speed with aqua 85KG/h, the fixed-bed reactor of squeezing into continuously the magnesium aluminum-hydrotalcite catalyzer that is mounted with nitrate radical intercalation after mixing through recycle pump, carry out esterification; Fixed-bed reactor control temperature is between 120 DEG C ~ 130 DEG C, and pressure-controlling is at 0.35MPa; The residence time of material in fixed-bed reactor is controlled at 20h; material after esterification enters dehydration tower and carries out distillation dehydration; controlling dehydration column overhead temperature is 80 DEG C; in the time that tower top does not have moisture content to distillate; material after dehydration is sent into acidylate still and carry out acidylate operation; after acidylate completes, carry out again the process for refining such as depickling, dehydration, finally obtain glycerine triacetate finished product.In the present embodiment, the chemical formula of the hydrotalcite catalyst of described polyacid intercalation is [Mg
6al
2(OH)
16] (P Mo
11coO
39)
35H
2o.
According to proportioning raw materials, theory obtains glycerine triacetate 663KG/h, the actual finished product 637KG/h that obtains, and yield is 96%.
In the present invention, utilize polyacid intercalation hydrotalcite or polyacid intercalation houghite to replace the liquid acid in traditional processing technology, utilize the character of the acid group of the special laminate structure of hydrotalcite and intercalation to realize catalytic effect, and recoverable, without the remaining liquid acid of neutralization, reduce wastewater flow rate, utilize environmental protection; And catalyzer service efficiency is high, can repeatedly use, the hydrotalcite catalyzer of 200Kg can be used in the catalytic production of 1000 tons of glycerine triacetates, the liquid acid of comparing, production cost greatly reduces.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a preparation technology for glycerine triacetate, is characterized in that, comprises the following steps:
A) glycerine, acetic acid and band aqua are pre-mixed, preheating, then enter the fixed-bed reactor that are loaded with the hydrotalcite of polyacid intercalation or the houghite of polyacid intercalation and carry out esterification;
B) above-mentioned esterification reaction product is sent into dehydration tower and carry out distillation dehydration, tower top temperature is 80 DEG C ~ 100 DEG C;
C) material after above-mentioned dehydration is sent into acidylate still, and add acylating agent to carry out acidylate, then the refining glycerine triacetate product that obtains.
2. the preparation technology of glycerine triacetate according to claim 1, is characterized in that, described hydrotalcite is the hydrotalcite that directly prepares undried; Divalent metal in the laminate of described hydrotalcite is Mg
2+, trivalent metal cation is Al
3+, interlayer anion is NO
3 -.
3. preparation method according to claim 2, is characterized in that, the chemical formula of the negatively charged ion of described polyacid is [XM
11coO
39]
n-, wherein X=P or Si; M=W or Mo; N is valence number, n=5-6.
4. the preparation technology of glycerine triacetate according to claim 1, is characterized in that, the mass ratio of described glycerine and acetic acid is 1:2.5 ~ 1:3.5.
5. the preparation technology of glycerine triacetate according to claim 1, is characterized in that, is describedly selected from the one in ethyl acetate, benzene, toluene with aqua, and the described consumption with aqua accounts for glycerine, acetic acid and with 5% ~ 10% of aqua total mass.
6. the preparation technology of glycerine triacetate according to claim 1, is characterized in that, described acylating agent is aceticanhydride, the consumption of described aceticanhydride be above-mentioned steps c) material after dewatering quality 3% ~ 8%.
7. the preparation technology of glycerine triacetate according to claim 1, is characterized in that, the condition of described acylation reaction is: 160 ~ 180 DEG C of acidylate temperature, the time is 1 ~ 2h.
8. the preparation technology of glycerine triacetate according to claim 1, is characterized in that, described esterification reaction temperature is 120 DEG C ~ 140 DEG C.
9. the preparation technology of glycerine triacetate according to claim 1, is characterized in that, the reaction time of esterification in described fixed-bed reactor is 20 ~ 30h.
10. for the preparation of a device for glycerine triacetate, it is characterized in that, comprise fixed-bed reactor and dehydration tower, the discharge end of described fixed-bed reactor is connected with the feed end of described dehydration tower; Described device also comprises bypass channel and acidylate still, and described bypass channel connects the dehydrated mouth of described dehydration tower, and described acidylate still connects the discharge port of described dehydration tower.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410187628.7A CN103965045B (en) | 2014-05-06 | 2014-05-06 | Preparation process and device for glycerol triacetate |
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|---|---|---|---|
| CN201410187628.7A CN103965045B (en) | 2014-05-06 | 2014-05-06 | Preparation process and device for glycerol triacetate |
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| CN103965045B CN103965045B (en) | 2015-05-13 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104744250A (en) * | 2014-12-15 | 2015-07-01 | 江苏雷蒙化工科技有限公司 | Method for synthesizing diacetylglycine |
| CN105399630A (en) * | 2015-12-31 | 2016-03-16 | 江苏瑞佳化学有限公司 | Method for preparing triethyl citrate through using nanometer intercalated hydrotalcite catalyst |
| CN105503594A (en) * | 2015-12-31 | 2016-04-20 | 江苏瑞佳化学有限公司 | Method for preparing acetyl tributyl citrate by nano scale intercalation hydrotalcite catalyst |
| CN105622404A (en) * | 2015-12-31 | 2016-06-01 | 江苏瑞佳化学有限公司 | Method for preparing isooctyl acetate through nanoscale intercalated hydrotalcite catalyst |
| CN106946698A (en) * | 2017-05-09 | 2017-07-14 | 江苏瑞晨化学有限公司 | A kind of method that utilization macromolecule loading mesoporous catalyst prepares triacetyl glycerine |
| CN107200686A (en) * | 2017-04-27 | 2017-09-26 | 南京工业大学 | A kind of method that utilization phenyl phosphate class bionic catalyst continuously produces acetoglyceride |
| CN114558339A (en) * | 2022-02-10 | 2022-05-31 | 南通百川新材料有限公司 | Novel esterification production equipment and method for n-propyl acetate |
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| CN102115444A (en) * | 2010-01-06 | 2011-07-06 | 江苏瑞佳化学有限公司 | Process and device for continuously producing glyceryl triacetate |
| CN103706403A (en) * | 2013-12-23 | 2014-04-09 | 北京化工大学 | Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate |
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| CN102115444A (en) * | 2010-01-06 | 2011-07-06 | 江苏瑞佳化学有限公司 | Process and device for continuously producing glyceryl triacetate |
| CN103706403A (en) * | 2013-12-23 | 2014-04-09 | 北京化工大学 | Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744250A (en) * | 2014-12-15 | 2015-07-01 | 江苏雷蒙化工科技有限公司 | Method for synthesizing diacetylglycine |
| CN105399630A (en) * | 2015-12-31 | 2016-03-16 | 江苏瑞佳化学有限公司 | Method for preparing triethyl citrate through using nanometer intercalated hydrotalcite catalyst |
| CN105503594A (en) * | 2015-12-31 | 2016-04-20 | 江苏瑞佳化学有限公司 | Method for preparing acetyl tributyl citrate by nano scale intercalation hydrotalcite catalyst |
| CN105622404A (en) * | 2015-12-31 | 2016-06-01 | 江苏瑞佳化学有限公司 | Method for preparing isooctyl acetate through nanoscale intercalated hydrotalcite catalyst |
| CN107200686A (en) * | 2017-04-27 | 2017-09-26 | 南京工业大学 | A kind of method that utilization phenyl phosphate class bionic catalyst continuously produces acetoglyceride |
| CN106946698A (en) * | 2017-05-09 | 2017-07-14 | 江苏瑞晨化学有限公司 | A kind of method that utilization macromolecule loading mesoporous catalyst prepares triacetyl glycerine |
| CN114558339A (en) * | 2022-02-10 | 2022-05-31 | 南通百川新材料有限公司 | Novel esterification production equipment and method for n-propyl acetate |
| CN114558339B (en) * | 2022-02-10 | 2024-02-02 | 南通百川新材料有限公司 | Esterification production equipment and method for n-propyl acetate |
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