CN108911976A - A kind of technique using p-methyl benzenesulfonic acid production acetate - Google Patents
A kind of technique using p-methyl benzenesulfonic acid production acetate Download PDFInfo
- Publication number
- CN108911976A CN108911976A CN201810494900.4A CN201810494900A CN108911976A CN 108911976 A CN108911976 A CN 108911976A CN 201810494900 A CN201810494900 A CN 201810494900A CN 108911976 A CN108911976 A CN 108911976A
- Authority
- CN
- China
- Prior art keywords
- methyl benzenesulfonic
- aqueous solution
- catalyst
- benzenesulfonic acid
- esterification
- 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
Classifications
-
- 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
Abstract
The present invention relates to a kind of techniques using p-methyl benzenesulfonic acid production acetate, solid Catalyzed by P-Toluenesulfonic Acid agent are added in deionized water, and stir and be configured to aqueous solution；Prepared aqueous solution pressurising is spare；Acetic acid and normal propyl alcohol is added in reaction kettle of the esterification, and catalyst aqueous solution is pressed into reaction kettle, be uniformly mixed and is heated up to 105 ~ 110 DEG C, the preparation of completion reaction bottom material.Its beneficial effect generated is that p-methyl benzenesulfonic acid esterification system corrosivity is significantly better than experimental result of the sulfuric acid as catalyst；P-methyl benzenesulfonic acid and the effect that reaction raw materials dissolve each other are relatively good；Catalyzed by P-Toluenesulfonic Acid agent does not need to add, and the loss of catalyst is few；The kettle liquid of Catalyzed by P-Toluenesulfonic Acid is still more limpid；Alcohol content is less in the thick ester that Catalyzed by p-Toluenesulfonic Acid reaction generates, and unknown material content 0.17% is obvious relatively low；The esterification waste liquid about 5ml that the esterification of Catalyzed by P-Toluenesulfonic Acid system generates, p-methyl benzenesulfonic acid are substantially better than sulfuric acid.
Description
Technical field
The present invention relates to esterification catalytic field more particularly to a kind of works using p-methyl benzenesulfonic acid production acetate
Skill.
Background technique
The catalyst that acid alcohol direct esterification reaction generallys use is aqueous sulfuric acid after dilution, and esterification is participated in aqueous solution
What is reacted is the hydrogen ion that sulfuric acid ionizes out；Although content of this catalyst aqueous solution in esterification kettle liquid only has 0.5% ~ 1%,
The features such as catalyst has catalytic reaction temperature low, and catalyst activity is high is always a kind of catalysis that esterification generally uses
Agent；But there are following several respects deficiencies for this kind of catalyst：1, acid corrosion is common problem existing for acidic catalyst；2, sulfuric acid
Catalyst has oxidation to reaction raw materials；3, sulfuric acid catalyst has dehydration property to reaction raw materials；4, sulfuric acid catalyst exists
Under conditions of certain, side reaction occurs with raw alcohol and generates the products such as sulfuric ester, hydrogen sulfuric acid ester.Rather than acid catalyst, although right
Equipment corrosion is very small, and the selectivity of reaction is also very high, and side reaction is fewer, but catalytic activity temperature is relatively high,
For example stannous oxide, titanate ester catalyst reactivity temperature are up to 180 DEG C or more, are generally only suitable for higher boiling reaction raw materials
Esterification.
Summary of the invention
It is unfavorable without the oxidisability of sulfuric acid etc. the purpose of the present invention is to provide a kind of suitable with sulfuric acid catalysis activity
In the technique using p-methyl benzenesulfonic acid production acetate of esterification.
To achieve the above object, the technique of the invention using p-methyl benzenesulfonic acid production acetate, it is characterised in that：
1, solid Catalyzed by P-Toluenesulfonic Acid agent is added in deionized water, and stirs and is configured to aqueous solution；
2, that prepared aqueous solution is pressurized to 0.3MPa is spare；
3, acetic acid and normal propyl alcohol is added in reaction kettle of the esterification（N-butanol）, and catalyst aqueous solution is pressed into reaction kettle, mixing is equal
It is even and be heated up to 105 ~ 110 DEG C, complete the preparation of esterification bottom material.
Preferably, when catalyst preparation, first deionized water is added in catalyst preparation kettle, until stirrer paddle can touch
Height, then the solid material after weighing is slowly added in catalyst preparation kettle from kettle top, while filling into deionized water, not
Disconnected stirring, is configured to aqueous solution.
Preferably, the concentration of aqueous solution is 30%.
Further, the acetate is n-propyl acetate and n-butyl propionate.
Preferably, the catalyst aqueous solution reaches 0.3MPa using nitrogen pressurising.
The advantage of the invention is that：
1, experimental result of the sulfuric acid as catalyst is significantly better than by coupon test p-methyl benzenesulfonic acid esterification system corrosivity；
2, reaction temperature is substantially suitable as the reaction temperature of catalyst with sulfuric acid also between 105 ~ 110 DEG C, and in this way
Within the temperature range of, hydrogen ion plays catalytic action, and p-methyl benzenesulfonic acid and the effect that reaction raw materials dissolve each other are relatively good；
3, sulfuric acid catalysis esterification proceeds to certain time, and catalytic capability weakens, and centre must add sulfuric acid catalyst, ability
Guarantee necessary catalytic capability；And the raw material reaction of the same scale of construction is carried out, Catalyzed by P-Toluenesulfonic Acid agent is not needed then to add, be urged
The loss of agent is few；
4, the kettle liquid of Catalyzed by P-Toluenesulfonic Acid is still more limpid；
5, alcohol content is less in the thick ester that Catalyzed by p-Toluenesulfonic Acid reaction generates, and unknown material content 0.17% is obvious relatively low；
6, the esterification waste liquid about 5ml that the esterification of Catalyzed by P-Toluenesulfonic Acid system generates, p-methyl benzenesulfonic acid are substantially better than sulfuric acid.
Specific embodiment
Technique using p-methyl benzenesulfonic acid production acetate of the invention, is replaced original using p-methyl benzenesulfonic acid
Sulfuric acid is reacted as catalyst, and entire reaction process is as follows：
The first step：Deionized water is added in catalyst preparation kettle, until the height that stirrer paddle can touch.
Second step：Solid material after weighing is slowly added in catalyst preparation kettle from kettle top, while filling into no ion
Water, and be stirred continuously, it is configured to the aqueous solution that concentration is 30%.
Third step：It is spare that configured aqueous solution using nitrogen is pressurized to 0.3MPa.
4th step：Acetic acid and normal propyl alcohol are added in reaction kettle of the esterification（N-butanol）, and catalyst aqueous solution is pressed into instead
It answers in kettle, be uniformly mixed and be heated up to 105 ~ 110 DEG C, the preparation of completion esterification bottom material.
Embodiment one：
Sulfuric acid and p-methyl benzenesulfonic acid are compared into test.
The sulfuric acid and 4g p-methyl benzenesulfonic acid for choosing 2g respectively pass through the first step in the above method and the as catalyst
The mode of two steps is configured to 30% aqueous solution, and the hydrionic concentration of aqueous solution is 0.04mol or so, and the concentration of catalyst is basic
Unanimously.
It recycles third step and the 4th step in the above method to carry out catalysis reaction, then persistently adds acetic acid and normal propyl alcohol
（N-butanol）Mixture is reacted, finally all obtains 2 kilograms containing the thick ester material of 86% or so acetate, result is examined after stopping reaction
It surveys as shown in table 1：
Table 1
| Catalyst | Acetate content | Unknown material content | Waste liquid amount | Kettle liquid situation |
| Sulfuric acid | 85.69% | 3.6% | 100mL | Dark thick |
| P-methyl benzenesulfonic acid | 86.11% | 0.17% | 5mL | It is limpid |
As seen from the above table, it compares sulfuric acid and p-methyl benzenesulfonic acid, the unknown material content and waste liquid amount of p-methyl benzenesulfonic acid is obviously low
In sulfuric acid, and p-methyl benzenesulfonic acid is significantly lower than sulfuric acid to the corrosivity of system, meanwhile, the kettle liquid of Catalyzed by P-Toluenesulfonic Acid
Still more limpid；And the esterification kettle liquid of sulfuric acid catalysis, color illustrate that side reaction relatively mostly occurs compared with being deeply in that black is thick；?
A 2g sulfuric acid was once added in sulfuric acid catalysis system in esterification process into reaction kettle of the esterification, maintains esterification to have higher anti-
It should be able to power.
In conclusion the catalytic effect of p-methyl benzenesulfonic acid is substantially better than sulfuric acid.
Embodiment two：
P-methyl benzenesulfonic acid carrys out the production process of catalytic esterification propyl acetate as shown in table 2-3 for 1%：
2 bottom material of table is esterified and is continuously added to mixture esterification
| Serial number | Time | Kettle temperature（℃） | It is esterified tower top temperature（℃） | Esterified state | Divide regimen condition | Remarks |
| 1 | 8：59 | Heating | ||||
| 2 | 9：12 | 100 | It comes to life | |||
| 3 | 9：18 | 101 | 83 | Tower top has water generation | ||
| 4 | 9：29 | 110 | 89 | There are a large amount of foams to generate in kettle | ||
| 5 | 9：42 | 111 | 99 | Separate moisture content 32ml | ||
| 6 | 10：22 | 114 | 102 | Mixture is added | ||
| 7 | 10：36 | 105 | 85 | Constantly there is elutriation to go out | ||
| 8 | 10：54 | 104 | 83 | Constantly there is elutriation to go out | ||
| 9 | 11：02 | 107 | 89 | Separate moisture content 31ml | Mixture adds | |
| 10 | 11：09 | Stop heating |
Table 3 is continuously added to mixture experiment
| Serial number | Time | Kettle temperature（℃） | It is esterified tower top temperature（℃） | Esterified state | Divide regimen condition | Remarks |
| 1 | 8：33 | Heating | Bottom pale solid precipitating | |||
| 2 | 8：50 | 110 | 100 | Overhead condensation liquid generates | A large amount of foams generate in kettle | |
| 3 | 8：56 | 109 | 98 | Tower top has water generation | Mixture is added | |
| 4 | 9：03 | 107 | 91 | Constantly there is elutriation to go out | ||
| 5 | 9：26 | 104 | 83 | Constantly there is elutriation to go out | ||
| 6 | 9：34 | 106 | 87 | Separate moisture content 26ml | ||
| 7 | 10：01 | 109 | 98 | Mixture is added | ||
| 8 | 10：02 | 106 | 90 | Constantly there is elutriation to go out | ||
| 9 | 10：09 | 106 | 88 | Separate moisture content 26ml | Mixture adds | |
| 10 | 10：17 | 106 | 85 | Constantly there is elutriation to go out | ||
| 11 | 10：28 | 106 | 86 | Constantly there is elutriation to go out | ||
| 12 | 10：37 | 106 | 86 | Separate moisture content 34ml | Mixture adds | |
| 13 | 10：59 | 112 | 102 | Stop heating |
As seen from the above table, catalysis reaction is carried out as catalyst using p-methyl benzenesulfonic acid, divides water close to theoretical yield
60mL, reaction effect are outstanding.
Embodiment three：
The production process of Catalyzed by P-Toluenesulfonic Acid esterification production n-butyl propionate is as shown in table 4-5：
4 bottom material esterification of table
| Serial number | Time | Kettle temperature | Depickling tower top temperature | Water yield | Remarks |
| 1 | 15：10 | 116℃ | 94℃ | ||
| 2 | 15：28 | 116℃ | 95℃ | ||
| 3 | 16：22 | 130℃ | Stop heating | 24ml |
Table 5 is tested with water for ester
Catalyst Catalyzed by P-Toluenesulfonic Acid esterification n-propyl acetate and n-butyl acetate it can be seen from embodiment two and three
When, all have the characteristics that high catalytic efficiency, is the acidic catalyst that substituted sulfuric acid catalytic esterification acetates are excellent at this stage；
In terms of experimental result above, it all has excellent in terms of to equipment corrosion, inhibition side reaction, catalyst
In the performance characteristics of sulfuric acid.
Claims (5)
1. a kind of technique using p-methyl benzenesulfonic acid production acetate, it is characterised in that：Include the following steps,
Solid Catalyzed by P-Toluenesulfonic Acid agent is added in deionized water, and stirs and is configured to aqueous solution；
It is spare that prepared aqueous solution is pressurized to 0.3MPa；
Acetic acid and normal propyl alcohol is added in reaction kettle of the esterification, and catalyst aqueous solution is pressed into reaction kettle, be uniformly mixed and is heated up to
105 ~ 110 DEG C, complete the addition of reaction bottom material.
2. the technique according to claim 1 using p-methyl benzenesulfonic acid production acetate, it is characterised in that：Catalyst is matched
When processed, first deionized water is added in catalyst preparation kettle, until the height that can touch of stirrer paddle, then by the solid after weighing
Material is slowly added in catalyst preparation kettle from kettle top, while filling into deionized water, and is stirred continuously, and aqueous solution is configured to.
3. the technique according to claim 2 using p-methyl benzenesulfonic acid production acetate, it is characterised in that：It is described water-soluble
Liquid concentration is 30%-50%.
4. the technique according to claim 1 using p-methyl benzenesulfonic acid production acetate, it is characterised in that：The acetic acid
Ester is n-propyl acetate and n-butyl propionate.
5. the technique according to claim 2 using p-methyl benzenesulfonic acid production acetate, it is characterised in that：The catalysis
Agent aqueous solution reaches 0.3MPa using nitrogen pressurising.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810494900.4A CN108911976A (en) | 2018-05-22 | 2018-05-22 | A kind of technique using p-methyl benzenesulfonic acid production acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810494900.4A CN108911976A (en) | 2018-05-22 | 2018-05-22 | A kind of technique using p-methyl benzenesulfonic acid production acetate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108911976A true CN108911976A (en) | 2018-11-30 |
Family
ID=64403467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810494900.4A Pending CN108911976A (en) | 2018-05-22 | 2018-05-22 | A kind of technique using p-methyl benzenesulfonic acid production acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108911976A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069964A (en) * | 1991-07-02 | 1993-03-17 | 联合碳化化学品及塑料技术公司 | Esterification process |
| CN101774912A (en) * | 2010-02-21 | 2010-07-14 | 南京荣欣化工有限公司 | Technology for producing acetic ester |
-
2018
- 2018-05-22 CN CN201810494900.4A patent/CN108911976A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069964A (en) * | 1991-07-02 | 1993-03-17 | 联合碳化化学品及塑料技术公司 | Esterification process |
| CN101774912A (en) * | 2010-02-21 | 2010-07-14 | 南京荣欣化工有限公司 | Technology for producing acetic ester |
Non-Patent Citations (1)
| Title |
|---|
| XINGJUN YAO ET.AL: "Fast Esterification of Acetic Acid with Short Chain Alcohols in Microchannel Reactor", 《CATALYSIS LETTERS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102775441B (en) | Continuous production method of glyphosate synthetic liquid | |
| TW201522380A (en) | Method for processing cellulose-containing biomass | |
| CN107188802A (en) | Using the method for the ionic liquid-catalyzed butyric ester of alcohol depolymerization 3 of bisgallic acid type | |
| He et al. | Continuous biodiesel production from acidic oil using a combination of cation-and anion-exchange resins | |
| CN105585455A (en) | Method of preparing ethylene glycol monomethyl ether through continuous etherification method | |
| Wilkinson et al. | A comparison of dilute acid-and alkali-catalyzed hydrothermal pretreatments for bioethanol production from brewers' spent grains | |
| CN104437637A (en) | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof | |
| CN101372605A (en) | Method for preparing rosin glyceride by microwave irradiation | |
| CN107189071B (en) | Preparation method of platinum catalyst for liquid silicone rubber | |
| CN108911976A (en) | A kind of technique using p-methyl benzenesulfonic acid production acetate | |
| CN103896772A (en) | Method for preparing glyceride by using catalytic esterification of glycerinum | |
| Ding et al. | Cation ion-exchange resin/polyethersulfone hybrid catalytic membrane for biodiesel production | |
| CN113198535B (en) | Preparation method of ceramic surface supported catalytic filler | |
| CN110389125A (en) | Application of the nano copper selenide as Mimetic Peroxidase detection hydrogen peroxide and L-cysteine | |
| CN102641746A (en) | Heteropolyacid modified catalyst, and preparation and catalyst catalytic hydrolysis reaction system thereof | |
| CN104844455A (en) | Method used for catalyzed synthesis of tert-butyl acrylate | |
| CN111423398A (en) | Method for preparing gamma-valerolactone from levulinic acid | |
| CN108435209B (en) | Preparation method of hydrophobic strong-acid carbon material | |
| CN106750364A (en) | The preparation method of lignin amine | |
| CN103623736B (en) | A kind of production equipment for environmental protection clean fuel and using method thereof | |
| CN110028602A (en) | A method of reducing impurity content in commercial polyethylene alcohol | |
| CN109603908A (en) | The method of Ni-based sulfonation zeolite organic backbone catalysis algae oil hydro-thermal aviation fuel | |
| CN102616924B (en) | Method for increasing biochemical treatment ability of printing and dyeing wastewater by utilizing enzyme activity soybean meal | |
| CN112851925B (en) | Preparation method of mixed phosphorus-containing polyol flame retardant | |
| CN113846128A (en) | Process flow for preparing biodiesel by liquid enzyme method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |