CN1569332A - solid catalyst for preparing dialkyl carbonate and application thereof - Google Patents
solid catalyst for preparing dialkyl carbonate and application thereof Download PDFInfo
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- CN1569332A CN1569332A CN 03145917 CN03145917A CN1569332A CN 1569332 A CN1569332 A CN 1569332A CN 03145917 CN03145917 CN 03145917 CN 03145917 A CN03145917 A CN 03145917A CN 1569332 A CN1569332 A CN 1569332A
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 27
- 239000011949 solid catalyst Substances 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000004927 clay Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 29
- 230000003197 catalytic effect Effects 0.000 claims description 13
- QQUZYDCFSDMNPX-UHFFFAOYSA-N ethene;4-methyl-1,3-dioxolan-2-one Chemical compound C=C.CC1COC(=O)O1 QQUZYDCFSDMNPX-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 26
- 230000009466 transformation Effects 0.000 description 18
- 238000004587 chromatography analysis Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 235000014380 magnesium carbonate Nutrition 0.000 description 4
- 229960001708 magnesium carbonate Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 206010003694 Atrophy Diseases 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a solid mixed catalyst, which comprises the following components: clay, metal carbonate and oxide thereof, wherein the ratio of the clay to the metal carbonate and the oxide thereof is (9-1) to 1. The invention also provides a preparation method of the catalyst and a method for synthesizing dialkyl carbonate by using the catalyst. The catalyst can make the active component of the catalyst firmly adsorbed on the clay, so that the reaction liquid does not contain catalyst components, the catalyst separation is not needed, the problem that the catalyst is difficult to recycle in the prior continuous reaction is solved, and the catalyst has higher activity and longer service life.
Description
Technical field
The present invention relates to a kind of solid compound catalyst and preparation method thereof, the invention still further relates to the method for utilizing this catalyzer synthesis of dialkyl carbonates.
Background technology
At present, the production method of dialkyl carbonate mainly contains three kinds: phosgenation, ester-interchange method and oxidative carbonylation method (comprising liquid phase method and vapor phase process), back two kinds of methods are non-phosgene.Because phosgenation exists shortcomings such as raw material severe toxicity, complex process, etching apparatus, contaminate environment, this production method is progressively atrophy.The oxidative carbonylation method is the employed main production method of present developed country.Ester-interchange method does not still have industrialized unit at present abroad, but it is the domestic production method that generally adopts.The characteristics of this method are that raw material is easy to get, technology is simple, yield is high, less investment, almost do not have the three wastes to produce.
In recent years, China has carried out development research widely to dialkyl carbonate, particularly the exploitation to methylcarbonate is quite extensive, mainly is to study around methyl alcohol (ME) and NSC 11801 (EC) and propylene carbonate (PC) transesterify Synthesis of dimethyl carbonate (DMC).In this reaction, generally all be to be catalyzer with alkali metal hydroxide, alkaline earth metal carbonate, alkali metal alcoholates.This type of catalyzer is a homogeneous catalyst, and catalyzer need separate and reclaim.And when separating catalyst, the alkane glycol of coproduction can be subjected to the influence of basic catalyst and take off water when high temperature, has directly influenced the yield and the economy of product.
All there is the report of this respect in some domestic research institutions.Chemical engineering institute of East China University of Science has delivered the article that is entitled as " preparing methylcarbonate with reaction rectification technique " in " Shandong petrochemical complex " first phase in 2002, reported the feasibility of successive reaction, obtain effect preferably, and applied for national patent.But this process using is homogeneous catalyst, exists the problem of catalyst separating difficulty.Coalification place, Chinese Academy of Sciences Shanxi " Speciality Petrochemicals " the 6th phase of calendar year 2001 has been delivered the article that is entitled as " catalytic performance that solid alkali is used for Synthesis of dimethyl carbonate ".University Of Tianjin has delivered the article that is entitled as " the catalytic distillation process of ester-interchange method Synthesis of dimethyl carbonate " in " petrochemical complex " third phase calendar year 2001, having reported with the 12-phospho-wolframic acid is the feasibility of the continuous catalyzing rectifying reaction of catalyzer, but transformation efficiency has only 45.28%.Catalyzer and processing condition see Table one.
Table one prior art catalyzer and processing condition synopsis
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of solid compound catalyst is provided; Provide also simultaneously that a kind of reaction process is short, the method for synthesis of dialkyl carbonates that must not separating catalyst.
Solid compound catalyst provided by the present invention, its component comprises: clay, metal carbonate and oxide compound thereof, the ratio of clay and metal carbonate and oxide compound thereof are (9-1): 1; Its preparation method is: clay and metal carbonate stir with distilled water, and after the granulation, maturing temperature progressively is warmed up to 600-1000 ℃, both obtain this catalyzer in roasting 4-6 hour.
Metal carbonate wherein can be alkaline carbonate or alkaline earth metal carbonate or its mixture.
Alkali-metal activity is better than the activity of alkaline-earth metal, and selectivity is slightly inferior to alkaline-earth metal, and its component concentration is high more, and activity is big more.
Preferred 800 ℃ of maturing temperature in this Preparation of catalysts method.
In roasting process, carbonate partly decomposes emits carbonic acid gas, becomes metal oxide.And emitting of carbonic acid gas increased the porosity of solid-phase catalyst, just increased the active ingredient passage.
The present invention also provides a kind of method for preparing dialkyl carbonate: with ethylene (propylene) carbonate and alcohol is raw material, adopts solid compound catalyst, through catalytic distillation prepared in reaction dialkyl carbonate.
Ethylene (propylene) carbonate among this preparation method can be NSC 11801 or propylene carbonate.
Catalytic distillation process in the preparation dialkyl carbonate is carried out in a packing tower, and its operational condition is:
(1) the catalytic distillation process is mainly carried out at the conversion zone of tower;
(2) mol ratio of raw alcohol and ethylene (propylene) carbonate is 6～10;
(3) the trim the top of column ratio is 0.5～5.0;
(4) atmospheric operation;
(5) tower still temperature is 70～130 ℃.
Wherein the preferred 70-100 of conversion zone temperature ℃, most preferably 90 ℃.Preferred 90 ℃ of tower still temperature wherein.Trim the top of column is than preferred 3.0.
Alcohol increases with the mol ratio of ethylene (propylene) carbonate, and the ethylene (propylene) carbonate transformation efficiency improves.But the cat head methanol content increases, and peeling strength is big, and is less economical, preferred 9: 1 of the mol ratio of alcohol and ethylene (propylene) carbonate among the present invention.
In reaction process,, the mixed type solid catalyst can be put into tower to tie up packet mode, both play the catalytic reaction effect, certain centrifugation is also arranged simultaneously for making better effects if.
The stage number of rectifying section, conversion zone, stripping section directly influences quality product.On the basis of condition experiment, determined that conversion zone plate number is the 20-50 piece, preferred 30; Rectifying section plate number is within 10～30 scopes; Stripping section plate number is within 5～20 scopes.
Below in conjunction with accompanying drawing 1, be that raw material is that example further specifies the present invention through catalytic distillation prepared in reaction methylcarbonate (DMC) with methyl alcohol (ME) with NSC 11801 (EC).
Accompanying drawing 1 is a catalytic distillation prepared in reaction DMC process flow sheet, wherein:
1-raw material EC import 2-raw material ME import
3-conversion zone top opening for feed 4-conversion zone underfeed mouth
The 5-DMC azeotrope goes the 6-of rectifying workshop section still liquid to go to rectifying workshop section
7-blow-down pipe G1-EC test tank
G2-ME test tank G3-DMC receiving tank
Y1-EC preheater Y2-ME producer gas generator
F1-still liquid withdrawing can F2-stripping section
F3-conversion zone F4-rectifying section
P1-EC charging stock tank P2-ME charging stock tank
E-condenser H-distribution of reflux device
Device mainly contains catalytic distillation Tower System, feed pump, basin, preheater etc. The catalytic distillation Tower System comprises tower reactor reboiler, stripping section, conversion zone, rectifying section, condenser etc. Tower reactor adopts coil pipe and outer wall insulation, and the packet mode catalyst is tied up in the conversion zone filling, is convenient to like this from the tower reactor heat-obtaining, and rectifying section and stripping section add dress angular thread filler, and condenser is equipped with counter flow controller.
Preparation process is mainly passed through several parts such as material preheating, material vaporization, catalytic reaction, rectifying separation, detailed process is as follows: catalyst provided by the invention is installed among the catalytic rectifying tower conversion zone F3, methyl alcohol (ME) 4 enters below F3 with gaseous form through gas generator Y2, and ethylene carbonate (EC) 3 enters above F3 with liquid form through feeder Y1. Methanol gas and the ethylene carbonate of vaporization are made counter current contacting in conversion zone, the dimethyl carbonate and the methanol gas that generate through ester exchange reaction are up to rectifying section F4, form with azeotropic mixture is isolated by cat head, and the ethylene carbonate of carrying secretly then goes downwards to conversion zone and continues to participate in reaction. By-product comprises diethylene glycol (DEG), triethylene glycol, methanol ethylene glycol ester, 1,1-dimethoxy-ethane, 1,2-dimethoxy-ethane etc. The ethylene carbonate of alkane glycol and trace, dimethyl carbonate, a small amount of methyl alcohol and micro-by-product then are advanced into down among the stripping section F2 of reaction fractionating tower, in stripping section, further isolate methyl alcohol and dimethyl carbonate, make it rise to again conversion zone and fully react. By the azeotropic mixture of the dimethyl carbonate of overhead collection and methyl alcohol to receiving tank G3, further separate to rectifying workshop section through 5 and to obtain product DMC, obtain byproduct alkane glycol with ME through further separating by the alkane two pure and mild ethylene carbonates of tower reactor collection and a small amount of dimethyl carbonate, methyl alcohol and dialkyl carbonate are delivered to rectifying workshop section, and ethylene (propylene) carbonate is sent the ethylene (propylene) carbonate basin back to and recycled.
Solid catalyst provided by the present invention can make the catalyst activity component be adsorbed on the clay securely, and this catalyst has higher activity and life-span, can continuous operation more than 1000 hours. In the preparation dialkyl carbonate, the conversion ratio of ethylene (propylene) carbonate reaches more than 80%, and the dialkyl carbonate productive rate reaches more than 75%, contains hardly catalyst component in the reactant liquor, so saved this step of separating catalyst when further separating tower bottoms. Shortened technological process, solved this engineering roadblock of separating catalyst, reaction can be carried out continuously.
Embodiment
The present invention is further described below by embodiment.
Preparation of catalysts:
Example 1
Get 225 gram clays, 25 gram salt of wormwood, add 50～80 gram water and stir, granulation then, particle size diameter is delivered in the muffle furnace again and was warmed up to 800 ℃ with 4 hours at 2～4mm, roasting 4～6 hours, the gained catalyzer is formed K
2O: K
2CO
3=1: 2.Adding a diameter is 25mm, and in the glass king-post of high 800mm, control reaction temperature is 70～100 ℃, successive reaction 6 hours, and the reaction solution gas chromatographic analysis, the DMC productive rate is 52%, the EC transformation efficiency is 60%.
Example 2
Get 210 gram clays, 90 gram salt of wormwood, add 40～60 gram water, all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 73%, the EC transformation efficiency is 85%.
Example 3
Get 150 gram clays, 150 gram salt of wormwood add 40～60 gram water, and all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 86%, the EC transformation efficiency is 95%.
Example 4
Get 225 gram clays, 25 gram magnesiumcarbonate, add 80～100 gram water and stir, all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 45%, the EC transformation efficiency is 50%.
Example 5
Get clay 210 gram, magnesiumcarbonate 90 grams, add 80～100 gram water and stir, all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 66%, the EC transformation efficiency is 75%.
Example 6
Get clay 150 gram, magnesiumcarbonate 150 grams, add 80～100 gram water and stir, all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 73%, the EC transformation efficiency is 79%.
Example 7
Get clay 200 gram, Strontium carbonate powder 50 grams, add 80～100 gram water and stir, all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 50%, transformation efficiency is 58%.
Example 8
Get clay 180 gram, Strontium carbonate powder 120 grams, add 80～100 gram water and stir, all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 62%, transformation efficiency is 69%.
Example 9
Get clay 200 gram, salt of wormwood 100 grams, magnesiumcarbonate 100 grams, add 80～100 gram water and stir, all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 79%, transformation efficiency is 87%.
Comparative Examples 1
Get 150 gram diatomite, 150 gram salt of wormwood add 40～60 gram water, and all the other are with example 1, the reaction solution gas chromatographic analysis, and the DMC productive rate is 59%, the EC transformation efficiency is 82%.
Table two evaluating catalyst synopsis
| Active ingredient | Active component content | DMC productive rate (%) | EC transformation efficiency (%) | |
| Embodiment 1 | ?K 2CO 3+K 2O | ????10 | ????52 | ????60 |
| Embodiment 2 | ?K 2CO 3+K 2O | ????30 | ????73 | ????85 |
| Embodiment 3 | ?K 2CO 3+K 2O | ????50 | ????86 | ????95 |
| Embodiment 4 | ?MgCO 3+MgO | ????10 | ????45 | ????50 |
| Embodiment 5 | ?MgCO 3+MgO | ????30 | ????66 | ????75 |
| Embodiment 6 | ?MgCO 3+MgO | ????50 | ????73 | ????79 |
| Embodiment 7 | ?SrCO 3+SrO | ????20 | ????50 | ????58 |
| Embodiment 8 | ?SrCO 3+SrO | ????40 | ????62 | ????69 |
| Embodiment 9 | ?K 2CO3+K 2O ?MgCO 3+MgO | ????50 | ????79 | ????87 |
| Comparative Examples 1 | ?K 2CO 3+K 2O | ????50 | ????59 | ????82 |
The preparation of dialkyl carbonate:
Embodiment 10
One main by conversion zone, rectifying tower section with carry and heating up in a steamer in the process unit that the tower section forms, drop into raw material EC and ME, raw material is during through reaction tower section catalyzer, the generation transesterification reaction is produced DMC.
Said reaction tower section is that diameter 25mm, height are the packing tower of 1000mm, and catalyzer is put into wherein to tie up packet mode.The conversion zone stage number is about 30.Said rectifying tower section is that diameter 45mm, height are the packing tower of 800mm, adopts stainless steel V-thread filler, and stage number is about 12.Said carrying heated up in a steamer the tower section and is diameter 25mm, high be the packing tower of 800mm, employing stainless steel V-thread filler, and stage number is about 12.
The temperature of reaction of conversion zone is controlled at about 70-100 ℃, and the stripping section temperature is controlled at about 90 ℃, and the rectifying section temperature is controlled at about 65-75 ℃.The control reflux ratio is 3.
Obtain analytical results, EC transformation efficiency 80%, DMC productive rate 72%.
Embodiment 11
Other conditions are constant, investigate the influence of proportioning raw materials to reaction.The mol ratio of methyl alcohol and EC is respectively 12/1 and at 6/1 o'clock, analytical results, the EC transformation efficiency is 84%, 70%, the DMC productive rate is 73.5%, 68%.Charge ratio increases, and the EC transformation efficiency improves, but the increase of cat head methanol content, peeling strength is big, and is less economical, determines that therefore the mol ratio of methyl alcohol and EC is 8.6: 1.
Embodiment 12
Other conditions are constant, investigate the influence of conversion zone temperature to reaction.Control reaction temperature is 80 ℃, 90 ℃, 100 ℃,, get analytical results, the EC transformation efficiency is 75%, 80%, 84%.The DMC productive rate is 70%, 72%, 71%.Along with the raising of temperature of reaction, the EC transformation efficiency improves, and selectivity reduces, and from balanced angle, the selective reaction temperature is an optimal reaction temperature for 90 ℃.
Claims (13)
1. solid compound catalyst, its component comprises: clay, metal carbonate and oxide compound thereof, the ratio of clay and metal carbonate and oxide compound thereof are (9-1): 1; Its preparation method is: clay and metal carbonate and oxide compound thereof stir with distilled water, and after the granulation, maturing temperature progressively is warmed up to 600-1000 ℃, roasting 4-6 hour, obtains this catalyzer.
2. the described catalyzer of claim 1 is characterized in that metal carbonate wherein is alkaline carbonate, alkaline earth metal carbonate or its mixture.
3. the described catalyzer of claim 1, it is characterized in that: catalyzer maturing temperature wherein is 800 ℃.
4. method for preparing dialkyl carbonate: with ethylene (propylene) carbonate and alcohol is raw material, adopts solid compound catalyst, through catalytic distillation prepared in reaction dialkyl carbonate.
5. preparation method as claimed in claim 4 is characterized in that ethylene (propylene) carbonate wherein is NSC 11801 or propylene carbonate.
6. preparation method as claimed in claim 4 is characterized in that said catalytic distillation process carries out in a tray column, be divided into three sections of conversion zones, rectifying section, stripping section, and the condition of its operation is:
(1) the catalytic distillation process is mainly carried out at the conversion zone of tower;
(2) mol ratio of the alcohol of charging and ethylene (propylene) carbonate is 6～10;
(3) the trim the top of column ratio is 0.5～5.0;
(4) working pressure is a normal pressure;
(5) tower still temperature is 70～130 ℃.
7. the described preparation method of claim 6 is characterized in that its board-like enriching section plate number is the 10-30 piece, and conversion zone plate number is the 20-50 piece, and stripping section plate number is the 5-20 piece.
8. preparation method as claimed in claim 6 is characterized in that rectifying section and stripping section add the filling material.
9. preparation method as claimed in claim 6 is characterized in that the conversion zone temperature is 70-100 ℃.
10. preparation method as claimed in claim 9 is characterized in that the conversion zone temperature is 90 ℃.
11. preparation method as claimed in claim 6 is characterized in that the alcohol and the mol ratio of ethylene (propylene) carbonate are 8.6: 1.
12. preparation method as claimed in claim 6 is characterized in that the mixed type solid catalyst puts into tower to tie up packet mode.
13. preparation method as claimed in claim 7 is characterized in that conversion zone plate number is 30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03145917 CN1283360C (en) | 2003-07-17 | 2003-07-17 | solid catalyst for preparing dialkyl carbonate and application thereof |
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| CN 03145917 CN1283360C (en) | 2003-07-17 | 2003-07-17 | solid catalyst for preparing dialkyl carbonate and application thereof |
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| CN1283360C CN1283360C (en) | 2006-11-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019192A (en) * | 2010-10-28 | 2011-04-20 | 内蒙古包钢和发稀土有限公司 | Process method for oil-free cerium carbonate serving as cleaning catalyst for automobile tail gas |
| CN109651153A (en) * | 2019-02-18 | 2019-04-19 | 西南化工研究设计院有限公司 | The method and its catalyst and preparation method of catalyst of a kind of synthesis of dialkyl carbonates |
| CN111170862A (en) * | 2020-01-10 | 2020-05-19 | 河北工业大学 | Method for preparing dimethyl carbonate by catalytic reaction rectification |
-
2003
- 2003-07-17 CN CN 03145917 patent/CN1283360C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019192A (en) * | 2010-10-28 | 2011-04-20 | 内蒙古包钢和发稀土有限公司 | Process method for oil-free cerium carbonate serving as cleaning catalyst for automobile tail gas |
| CN102019192B (en) * | 2010-10-28 | 2013-07-03 | 内蒙古包钢和发稀土有限公司 | Process method for oil-free cerium carbonate serving as cleaning catalyst for automobile tail gas |
| CN109651153A (en) * | 2019-02-18 | 2019-04-19 | 西南化工研究设计院有限公司 | The method and its catalyst and preparation method of catalyst of a kind of synthesis of dialkyl carbonates |
| CN111170862A (en) * | 2020-01-10 | 2020-05-19 | 河北工业大学 | Method for preparing dimethyl carbonate by catalytic reaction rectification |
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| CN1283360C (en) | 2006-11-08 |
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