CN1005133B - Solid acid catalyst for producing glycol ethers - Google Patents
Solid acid catalyst for producing glycol ethers Download PDFInfo
- Publication number
- CN1005133B CN1005133B CN85104661.4A CN85104661A CN1005133B CN 1005133 B CN1005133 B CN 1005133B CN 85104661 A CN85104661 A CN 85104661A CN 1005133 B CN1005133 B CN 1005133B
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- CN
- China
- Prior art keywords
- solid acid
- acid catalyst
- zsm
- molecular sieve
- exchange
- 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.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 239000011973 solid acid Substances 0.000 title claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title description 10
- -1 glycol ethers Chemical class 0.000 title description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title description 2
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 238000003746 solid phase reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 235000013312 flour Nutrition 0.000 description 6
- 230000009466 transformation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A solid acid catalyst for preparing glycol ether is prepared from ZSM-5 molecular sieve through ion exchange with inorganic acid or the salt solution of Zn, Mg, Fe, etc. The conversion rate of the ethylene oxide is close to 100 percent and the yield of the glycol ether reaches 75 to 90 percent after the reaction is carried out for 30 to 40 minutes at 100 to 150 ℃ by adding 5 percent of solid acid catalyst into the aliphatic alcohol of the ethylene oxide and the C ↓ [ 4 ] -C ↓ [ 4 ] with the gram-molecule ratio of 1: 4 to 1: 9.
Description
The present invention relates to a kind of is the solid acid catalyst of parent with the ZSM-5 molecular sieve, and uses this catalyzer to produce the production method of gylcol ether.
Industrial production gylcol ether generally is to adopt oxyethane and C
1-C
4Lower aliphatic alcohols be raw material, in the presence of catalyst-free or acid, alkaline catalysts, synthesize, it is actual carry out following all reactions are arranged:
Main reaction:
-OH → ROC
2H
4The OH monoether
CH
2-CH
2
Side reaction: 2 O+R-OH → ROC
2H
4OC
2H
4The OH diether
CH
2-CH
2
O+ROC
2H
4OH → ROC
2H
4OC
2H
4The OH diether
CH
2-CH
2
O+R·O·C
2H
4·OC
2H
4OH→
ROC
2H
4OC
2H
4OC
2H
4OH three ethers
……
CH
2-CH
2
O+H
2O → HOCH
2CH
2OH ethylene glycol
N O → (CH
2-CH
2O) n polyoxyethylene glycol
In reaction, the yield of glycol ether (hereinafter to be referred as monoether) depends on oxyethane and the ratio of alcohol, the performance and the synthetic condition of catalyzer in the reactant.At present, the industrial liquid acid catalyst that adopts (as BF more
3, H
2SO
4, H
3PO
4Deng), but its side reaction is many, and catalyzer and product be at same internal reaction mutually, and catalyzer is not easily separated and reclaim, and just can carry out rectification and purification after need adding acid in the alkali neutralized reaction product.In addition, liquid acid is to the corrosion of equipment, and waste liquid all is bothersome problem to the pollution of environment.Adopt solid acid can overcome above-mentioned shortcoming.As U.S. Pat .P1011268(1977), Japanese Patent: day special public clear 38-4859, once report the employing macroporous ion exchange resin with special public clear 52-89606 of day and made catalyzer, glycol ether synthetic had higher selectivity, by product is greatly reduced, and catalyzer is easy to separate with product, again non-corrosiveness and be easy to serialization production, but its per pass conversion is lower, only is 37%.It is Primary Catalysts that the public clear 54-106409 of Japanese Patent has reported first with ZrO, Sn
2O
3, ZnO is the composite oxide catalysts of promotor, but its alcohol is too big with feed ratio of oxyethane, thereby efficient is not high.
In order to solve the above-mentioned gylcol ether variety of issue in producing, we adopt the ZSM-5 molecular sieve is parent, carries out making solid acid catalyst after the ion-exchange with high price salts solutions such as mineral acid (for example hydrochloric acid or nitric acid) or its magnesium, zinc, iron.If using mole ratio is 1: 4-1: the mixture of 9 oxyethane and alcohol (containing 1-4 carbon atom), at 100-150(℃) temperature range in react, then can obtain the glycol ether that yield is 70-90%.
The prepared solid acid catalyst of the present invention has tangible solid acid katalysis, can be used as the catalyst for reaction such as cracking, hydrocarbonylation, disproportionation, isomerization of hydro carbons; Because the ZSM-5 molecular sieve has 5-6
Three-dimensional netted pore texture, have 500m
2The surface-area of/g so reactant can free spread, react and be not easy to polymerization, coking, thereby has the catalytic life of growing in the hole; Because the ZSM-5 molecular sieve has higher SiO
2/ Al
2O
3Ratio, there is certain hydrophobic nature on its surface, thereby water content exerts an influence hardly to reaction in the reaction.Adopting this solid acid catalyst to produce gylcol ether (is example with the ethylene glycol ethyl ether) has the following advantages:
1. catalyst activity height, after feeding intake 20-30 minute, reaction can be finished, and the transformation efficiency of oxyethane is near 100%.The monoether yield reaches 70-90%.
2. selectivity is good, and the moisture content of alcohols and reacting ethylene oxide are less in reaction, so can use industrial alcohol to make raw material, has reduced productive expense.And the growing amount of its by product-ethylene glycol is less when adopting catalyzer of the present invention, and this has just reduced the difficulty (being difficult to isolating azeotrope because ethylene glycol and diether can form) of rectifying separation diether.
3. this solid acid catalyst is easy to Separation and Recovery, and repeatedly recycling does not need regeneration and activation, and product is not with acidity, can add the alkali neutralization.
4. this solid acid catalyst does not corrode equipment, environmentally safe.
5. the used ZSM-5 molecular sieve of the present invention is that Chemical Plant of Nankai Univ. produces with " direct method ", and it is lower than molecular sieve performance excellence and its price of producing with " amine process ".
6. when using this catalyzer to carry out various chemical reaction its technology simple, be easy to operate and control, also can carry out continuous flow production.
Manufacturing and application thereof for this catalyzer is described are exemplified below (used ZSM-5 molecular sieve is Chemical Plant of Nankai Univ.'s " direct method " synthetic in the example);
Example 1:
In 50 liter reactors, add SiO
2/ Al
2O
3Be that 38 ZSM-5 molecular sieve and the HCl(molecular sieve of 0.3N and the weight ratio of acid solution are 1: 2), in stir in 80-90 ℃ scope, keep 2 hours down after, filter, wash with water to pH=4-5,120 ℃ of oven dry down, gained crystalline flour rerum natura is as follows:
Na
2O content 0.20%
Normal hexane adsorptive capacity 11%
SiO
2/Al
2O
339.20
Add the clay of 10-30% toward above-mentioned crystalline flour, in 120 ℃ of bakings 4 hours down, 550 ℃ of following calcinations 3 hours are solid acid catalyst of the present invention after the moulding.
Example 2:
In 50 liter enamel reactors, add SiO
2/ Al
2O
3=38 ZSM-5 molecular sieve and 0.3 zinc nitrate, the weight ratio of molecular sieve and zinc nitrate are 1: 2, and under agitation, in 95 ℃, constant temperature leached acid solution after 1.5 hours, wash with water to pH=4-5, and gained Zn type ZSM-5 crystalline flour rerum natura is as follows:
Na
2O content 0.003%
Normal hexane adsorptive capacity 12.5%
SiO
2/Al
2O
341.92
Dried 4 hours down in 120 ℃ behind the clay of adding 10-30% and the above-mentioned crystalline flour mixing moulding, 550 ℃ of following calcinations promptly obtained solid acid catalyst of the present invention in 3 hours.
Example 3:
Use SiO
2/ Al
2O
3=27 ZSM-5 molecular sieve and HCl or the Zn(NO of 0.3N
3)
2According to the switching method of example 1 and example 2, gained ZSM-5 crystalline flour rerum natura is as follows:
Na
2O content＜0.055%
Normal hexane adsorptive capacity 11.7%
SiO
2/Al
2O
330
Toward the clay of ZSM-5 crystalline flour adding 10-30%, to dry 4 hours down at 120 ℃ after the moulding, 550 ℃ of following calcinations promptly obtained solid acid catalyst of the present invention in 3 hours.
Example 4:
With mole ratio is that 1: 5 oxyethane and dehydrated alcohol mixed solution 150 gram input capacity are in 200 milliliters the reactor, adds the solid acid catalysts of 7.5 grams, and sealing is placed in 120 ℃ the oil bath, reacts postcooling discharging in 30 minutes.Prove that by analysis the oxyethane transformation efficiency is 100%.The productive rate of ethylene glycol ethyl ether is 85%.
Example 5:
Reactions steps is with example 4, with mole ratio is that 1: 6 oxyethane and industrial alcohol (moisture 5-8%) mixed solution 150 gram input capacity are in 200 milliliters the reactor, add 10 gram solid acid catalysts, after reacting 30 minutes under 120 ℃, the transformation efficiency of oxyethane is 99%, and the ethylene glycol ethyl ether productive rate is 80% to 85%.
Example 6:
Reactions steps is with example 4, and the adding mole ratio is 1: 8 oxyethane and dehydrated alcohol mixture 150 grams, adds catalyzer 7.5 grams again, and reaction is after 30 minutes down at 105 ℃, and the transformation efficiency of oxyethane is 100%, and the productive rate of ethylene glycol ethyl ether is 98%.
Example 7:
In the reactor of 60 liters, processing industry ethanol 24.5kg, solid acid catalyst 1.5kg and oxyethane 4.4kg reacted after 30-40 minute, and the oxyethane transformation efficiency is 99%, and the ethylene glycol ethyl ether productive rate is 77%, and residual catalyst can use repeatedly.
Example 8:
Routine remaining catalyzer in the application, reactions steps and material proportion are with example 7, and temperature of reaction is 100-110 ℃, react that the ethylene glycol ethyl ether productive rate is 78.10% after 40 minutes.
Claims (3)
1, a kind of solid acid catalyst that is suitable for the liquid-solid phase reaction, it is characterized in that it be a kind of be parent with the ZSM-5 molecular sieve, carry out ion-exchange through cationic saline solutions of high price such as mineral acid or Mg, Zn, Fe, the clay that adds 10-30% then is that tackiness agent makes its moulding, and in 120 ℃ of oven dry down, under 500-600 ℃ temperature, carry out calcination and make its SiO
2/ Al
2O
3Be 20-60, Na
2O content is less than 0.5%, and granularity is the 10-30 order.
2,, it is characterized in that the SiO of used ZSM-5 according to the said solid acid catalyst of claim 1
2/ Al
2O
3Can be in the scope of 20-60, the medium that is used for ion-exchange is the hydrochloric acid of 0.3N or the nitrate of metals such as Mg, Zn, Fe, the weight ratio of ZSM-5 molecular sieve and acid solution is 1: 2, and the temperature when carrying out ion-exchange is 80-100(℃), be 1-2 hour swap time.
3, can be used to prepare ethylene glycol ethyl ether according to claim 1 and/or 2 said catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104661.4A CN1005133B (en) | 1985-06-14 | 1985-06-14 | Solid acid catalyst for producing glycol ethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104661.4A CN1005133B (en) | 1985-06-14 | 1985-06-14 | Solid acid catalyst for producing glycol ethers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104661A CN85104661A (en) | 1987-07-08 |
| CN1005133B true CN1005133B (en) | 1989-09-13 |
Family
ID=4793983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85104661.4A Expired CN1005133B (en) | 1985-06-14 | 1985-06-14 | Solid acid catalyst for producing glycol ethers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005133B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033742C (en) * | 1991-07-10 | 1997-01-08 | 南开大学 | Solid strengthened catalyst for preparation of glycol ether |
| US8536083B2 (en) | 2004-09-01 | 2013-09-17 | Shell Oil Company | Olefin epoxidation process, a catalyst for use in the process, a carrier for use in preparing the catalyst, and a process for preparing the carrier |
| JP5063367B2 (en) * | 2005-02-21 | 2012-10-31 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Olefin epoxidation process, catalyst used in the process, support used in making the catalyst, and process for making the support |
| CN102266763A (en) * | 2010-06-04 | 2011-12-07 | 南京工程学院 | Solid alkaline catalyst for synthesis of 1-methoxy-2-propanol, and preparation method thereof |
| CN102795637B (en) * | 2011-05-26 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of exchange method of modifying reducing sodium oxide content in type ZSM 5 molecular sieve |
| CN102964223A (en) * | 2012-11-13 | 2013-03-13 | 宁波杭州湾新区珠峰企业管理服务有限公司 | Preparation method of propylene glycol monomethyl ether |
| WO2016187773A1 (en) * | 2015-05-25 | 2016-12-01 | 高化学株式会社 | Catalyst for preparing glycol ether and preparation method and application thereof |
| CN105688881B (en) * | 2016-02-25 | 2018-07-31 | 洛阳市科创石化科技开发有限公司 | A kind of catalyst and its preparation method and application of synthesis alkylene glycol ether |
| CN106631712A (en) * | 2016-11-23 | 2017-05-10 | 山东玉皇化工有限公司 | Preparation method of ethylene glycol monobutyl ether |
| CN109092349A (en) * | 2017-06-20 | 2018-12-28 | 高化学技术株式会社 | It is used to prepare the catalyst and its preparation method and application of glycol dimethyl ether |
-
1985
- 1985-06-14 CN CN85104661.4A patent/CN1005133B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104661A (en) | 1987-07-08 |
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