CN103357426A - Preparation method of solid strong acid and catalysis prompting function thereof in process of preparing chloroacetic acid by using acetic anhydride catalysis method - Google Patents
Preparation method of solid strong acid and catalysis prompting function thereof in process of preparing chloroacetic acid by using acetic anhydride catalysis method Download PDFInfo
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- CN103357426A CN103357426A CN2013102954683A CN201310295468A CN103357426A CN 103357426 A CN103357426 A CN 103357426A CN 2013102954683 A CN2013102954683 A CN 2013102954683A CN 201310295468 A CN201310295468 A CN 201310295468A CN 103357426 A CN103357426 A CN 103357426A
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Abstract
The invention relates to a preparation method of a solid strong acid. The preparation method is characterized by comprising the following steps of: taking a n-butyl alcohol solution of tetrabutyl titanate and Zr(OBu)4, mixing the n-butyl alcohol solution of ethanol, uniformly mixing, subsequently adding an ethanol solution of lauryl amine, and dropping a 95% ethanol water solution, wherein white precipitate is precipitated out in the dropping process, after the precipitation is accomplished, filtering, cleaning by using ethanol, drying white solid, calcining so as to obtain a catalyst precursor TiO2-ZrO2; dipping the catalyst precursor TiO2-ZrO2 in an ammonium sulfate solution, filtering, drying in vacuum to be constant weight, calcining for 1-5 hours at 300-600 DEG C so as to obtain a solid super-strong acid SO42-/TiO2-ZrO2; reacting for 1.5-5 hours at 90-120 DEG C by taking an acetic acid and a chlorine gas as raw materials, taking acetic anhydride as a catalyst and taking the solid strong acid SO42-/TiO2-ZrO2 as a catalysis prompter so as to obtain a chloroacetic acid. The preparation method is short in process reaction time, high in reaction operability and simple in process, and good activity and selectivity are achieved.
Description
Technical field
The present invention relates to the preparation method of solid strong acid and prepare the promoting catalysis of monoxone technique at the acetic anhydride catalysis method.
Background technology
Monoxone (MCA) has another name called chloroacetic acid, is a kind of important organic chemical industry's intermediate.It is widely used in the production of agricultural chemicals, medicine, dyestuff and multiple organic chemistry product.Chloroacetic production method is more, mainly contains Catalytic Chlorination of acetic acid method, trichloro-ethylene Hydrolyze method, vinyl chloride oxidizing process, chlorethanol oxidizing process, chloracetyl chloride Hydrolyze method, ketenes chloridising and tetrachloroethanes Hydrolyze method.The chloroacetic method of present industrial production mainly contains two kinds.A kind of is the trichloro-ethylene Hydrolyze method, and this method can obtain highly purified monoxone, but consumption of raw materials is larger, and operation is long, and cost is high; Another kind is the acetic acid catalytic chlorination process, and this method technique is simple, invests littlely, and cost of material is relatively low and easily obtain, but reaction control relative difficulty is larger, and product easily contains many chloroacetic acids.Produce monoxone with domestic most employing acetic acid catalytic chlorination process in the world at present.
Acetic acid chlorination method mainly is divided into sulphur catalytic chlorination process and acetic anhydride catalysis chloridising.The sulphur catalytic chlorination process is technique early, although comparative maturity, relative activity and selectively lower, and also residual sulphur has affected chloroacetic quality in the product.The advantages such as the acetic anhydride catalysis method is the advanced production of chloroacetic acid method of generally acknowledging at present, and it is good that it has catalytic activity, and product quality is high, and environmental pollution is little.External main this explained hereafter monoxone that adopts, China is also as the one preferred technique route that increases production of chloroacetic acid newly.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of solid strong acid, this solid strong acid is used for the acetic anhydride catalysis method as co-catalyst and prepares monoxone technique, have good selective, and the reaction time significantly shorten.
The preparation method of solid strong acid may further comprise the steps:
(1) takes by weighing the butyl titanate [Ti (OBu) of 1.0 weight portions
4] and the mass fraction of 1.4 weight portions be 80%Zr (OBu)
4Butanol solution, be dissolved in the ethanol, after mixing, add the ethanolic solution (concentration is without specific (special) requirements) of the lauryl amine of 0.56 weight portion, then drip 95% ethanol water.Adularescent Precipitation in the dropping process after precipitation is finished, precipitate 12 hours, and with the ethanol washing, white solid was calcined 4 hours at 550 ℃ in 80 ℃ of dryings 10 hours, obtained catalyst precarsor TiO after filtering
2-ZrO
2
(2) the catalyst precarsor TiO that step (1) is obtained
2-ZrO
2Dipping is 2-10 hour in ammonium sulfate, filters, and to constant weight, 300-600 ℃ obtained solid super-strong acid SO in roasting 1-5 hour 70-100 ℃ of vacuum drying
4 2-/ TiO
2-ZrO
2Catalyst precarsor TiO
2-ZrO
2With the mol ratio of ammonium sulfate be 1:0.2～3.0.
The acetic anhydride catalysis method prepares chloroacetic technique, is take acetic acid and chlorine as raw material, take acetic anhydride as catalyst, and solid strong acid SO
4 2-/ TiO
2-ZrO
2As co-catalyst, 90～120 ℃ of reactions obtained monoxone, preferable reaction temperature 95-110 ℃ in 1.5～5 hours.
Acetic acid in the reaction system: acetic anhydride: solid strong acid SO
4 2-/ TiO
2-ZrO
2Mass ratio be 100:3～15:0.1～5.
Adopt more than one during reaction, better 3 reactor cascade reactions, when the liquid height in the previous reactor reached the liquid outlet of reactor, then liquid entered next reactor continuation reaction, and last reactor liquid out enters the separator separation and obtains the finished product monoxone.Piece-rate system comprises the hydrogenation apparatus of common one or more levels cooling device and many chlorine product.The liquid outlet of each reactor is provided with corrosion resistant network of micropores envelope, can effectively stop the loss of solid strong acid co-catalyst.
The reaction system autoreaction liquid of the present patent application enters reactor and finishes to reaction, reaction time range 1.5～5 hours, with respect to only use acetic anhydride to make catalyst to need 12 hours reaction time (Xu Yanli, petrochemical industry, 1998(5); 313-318), reaction rate is significantly improved, and has following characteristic:
1. need not to use activated carbon supported, reduced the amount of insoluble matter in the reaction system, the load of equipment is alleviated, be more conducive to operation.The reactant liquor reaction time that another progress is present patent application namely reaches activated carbon supported other types solid strong acid such as SO about 3 hours
4 2-/ MxOy or S
2O
8 2-The conversion ratio of the little the reaction time of/MxOy6 has the high advantage of obvious monoxone generating rate.
2. the catalyst system of present patent application has good selectively, and the generation of its dichloroacetic acid is no more than 3.0%.
3. reaction process is simple, and the series connection form for reactor is beneficial to the realization continued operation, and can energy efficient.
4. easy technique makes this catalyst system and catalyzing and the corresponding process route can be handling strong.
The specific embodiment
The below places each reactor take 3 reactor series connection as example describes with the strong acid co-catalyst, and addition is the 0.1-5% of the effective volume of reactor.
Embodiment 1
The preparation process of solid strong acid is as follows: take by weighing 3.4g butyl titanate [Ti (OBu)
4] and the 4.76g mass fraction be 80%Zr (OBu)
4Butanol solution, be dissolved in the 40ml ethanol, after mixing, add the solution of the 1.9g lauryl amine be dissolved in 40ml ethanol, then drip the ethanolic solution of 80ml95%.Adularescent Precipitation in the dropping process, after precipitation is finished, ageing 12 hours, with ethanol washing three times, white solid is in 80 ℃ of dryings 10 hours after filtering, and 550 ℃ of calcinings 4 hours obtain 2.1g TiO
2-ZrO
2The co-catalyst precursor.With catalyst precarsor TiO2-ZrO2 at ammonium sulfate (catalyst precarsor TiO
2-ZrO
2With the mol ratio of ammonium sulfate be 1:0.2) in dipping 8 hours, filter, to constant weight, 300 ℃ of roastings obtained solid strong acid SO in 1 hour 70 ℃ of vacuum drying
4 2-/ TiO
2-ZrO
2
The acetic anhydride catalysis method prepares monoxone: connect three reactors, the reactor effective volume is 50ml, is exactly the following volume of net envelope overfall, with 1g solid strong acid co-catalyst SO
4 2-/ TiO
2-ZrO
2Equivalent is added in three reactors respectively, and fills it up with respectively reactor with reactant liquor in the head tank.Acetic acid and acetic anhydride batching mass ratio is that 10:1(is respectively 100g, 10g in the head tank).In order to make reactive flow unimpeded, the pressure that adds chlorine in head tank is adjusted into 0.05～0.1MPa, also can utilize potential difference to make reactant liquor enter reactor, regulate the raw material flow rate of exit valve control reactor, among this embodiment in the control head tank reactant liquor enter into speed 2ml/ minute of reactor, the temperature of controlling in three reactors is 100 ℃.All pass into chlorine from the bottom with the multiple exit pipe in three reactors, react after 2 hours, collect continuously product 10min and measure by analysis catalytic effect: acetic acid 65.30wt%, monoxone 33.49wt%, dichloroacetic acid 1.21wt%, conversion ratio is with acetometer 21.1.%.
Embodiment 2
The temperature of controlling in three reactors is 110 ℃, and reactant liquor enters into speed 1.2ml/ minute of reactor in the head tank, and all the other conditions all are same as embodiment 1, react after 3 hours, collect continuously product 10min, and the mensuration component is wt%; Acetic acid 37.42%, monoxone 61.30%, dichloroacetic acid 1.28%, conversion ratio is with acetometer 38.62%.
Embodiment 3
The temperature of controlling in three reactors is 120 ℃, and to enter into the speed of reactor be 1.0ml/ minute to reactant liquor in the head tank, and all the other conditions all are same as embodiment 1, react after 5 hours, collect continuously product 20min, and the mensuration component is wt%; Acetic acid 0.81%, monoxone 96.44%, dichloroacetic acid 2.75%, conversion ratio is with acetometer 60.76%.
Embodiment 4
The temperature of controlling in three reactors is 90 ℃, and to enter into the speed of reactor be 1.5ml/ minute to reactant liquor in the head tank, and all the other conditions all are same as embodiment 1, react after 2.5 hours, collect continuously product 5min, and the mensuration component is wt%; Acetic acid 69.20%, monoxone 29.60%, dichloroacetic acid 1.20%, conversion ratio is with acetometer 18.65%.
Embodiment 5
The temperature of controlling in three reactors is 105 ℃, and to enter into the speed of reactor be 2.6ml/ minute to reactant liquor in the head tank, and all the other conditions all are same as embodiment 1, react after 1.5 hours, collect continuously product 10min, and the mensuration component is wt%; Acetic acid 67.2%, monoxone 30.8%, dichloroacetic acid 2.0%, conversion ratio is with acetometer 19.4%.
Embodiment 6
The acetic anhydride catalysis method prepares chloroacetic reaction; Acetic acid and acetic anhydride and solid strong acid SO in the control head tank
4 2-/ TiO
2-ZrO
2The batching mass ratio is 100:3:2, catalyst precarsor TiO in the step (2)
2-ZrO
2With the mol ratio of ammonium sulfate be dipping 10h hour among the 1:2, filter, to constant weight, 600 ℃ of roastings obtained solid strong acid SO in 3 hours 100 ℃ of vacuum drying
4 2-/ TiO
2-ZrO
2All the other conditions all are same as embodiment 1, measure component wt%; Acetic acid 64.8%, monoxone 33.6%, dichloroacetic acid 1.6%, conversion ratio is with acetometer 21.17%.
Embodiment 7
The acetic anhydride catalysis method prepares chloroacetic reaction: acetic acid and acetic anhydride and solid strong acid SO in the control head tank
4 2-/ TiO
2-ZrO
2The batching mass ratio is 100:15:5, catalyst precarsor TiO in the step (2)
2-ZrO
2With the mol ratio of ammonium sulfate be dipping 2h hour among the 1:3, filter, to constant weight, 500 ℃ of roastings obtained solid strong acid SO in 5 hours 80 ℃ of vacuum drying
4 2-/ TiO
2-ZrO
2All the other conditions all are same as embodiment 1, measure component wt%; Acetic acid 0.36%, monoxone 97.56%, dichloroacetic acid 2.08%, conversion ratio is with acetometer 61.46%.
Claims (9)
1. the preparation method of solid strong acid is characterized in that may further comprise the steps:
(1) gets butyl titanate and Zr (OBu)
4Butanol solution, all be mixed in the ethanol, after mixing, add the ethanolic solution of lauryl amine, then drip 95% ethanol water.Adularescent Precipitation in the dropping process after precipitation is finished, filters, and with the ethanol washing, white solid is dry, calcining, obtains catalyst precarsor TiO
2-ZrO
2
(2) the catalyst precarsor TiO that step (1) is obtained
2-ZrO
2Flood in ammonium sulfate, filter, vacuum drying is to constant weight, and 300-600 ℃ obtained solid super-strong acid SO in roasting 1-5 hour
4 2-/ TiO
2-ZrO
2
2. the preparation method of solid strong acid according to claim 1 is characterized in that the butyl titanate of per 1 weight portion in the step (1), and the mass fraction that takes by weighing 1.4 weight portions is 80% Zr (OBu)
4The ethanolic solution of lauryl amine of butanol solution, 0.56 weight portion.
3. the preparation method of solid strong acid according to claim 1 is characterized in that step (1) gained white precipitate is 80 ℃ of dryings 10 hours, 550 ℃ of calcinings 4 hours.
4. the preparation method of solid strong acid according to claim 1 is characterized in that step (2) dip time 2-10 hour, and the vacuum drying temperature is 70-100 ℃; Catalyst precarsor TiO
2-ZrO
2With the mol ratio of ammonium sulfate be 1:0.2～3.0.
5. claim 1 gained solid strong acid prepares in the chloroacetic technique as the application of co-catalyst at the acetic anhydride catalysis method, is take acetic acid and chlorine as raw material, take acetic anhydride as catalyst, and solid strong acid SO
4 2-/ TiO
2-ZrO
2As co-catalyst, 90～120 ℃ of reactions obtained monoxone in 1.5～5 hours.
6. described solid strong acid prepares in the chloroacetic technique as the application of co-catalyst at the acetic anhydride catalysis method according to claim 5, it is characterized in that acetic acid, acetic anhydride, solid strong acid SO
4 2-/ TiO
2-ZrO
2Mass ratio be 100:3～15:0.1～5.
7. described solid strong acid prepares in the chloroacetic technique application as co-catalyst at the acetic anhydride catalysis method according to claim 5, adopt the form of an above reactor series connection when it is characterized in that reacting, last reactor liquid out enters the separator separation and obtains the finished product monoxone.
8. the gained solid strong acid prepares in the chloroacetic technique as the application of co-catalyst at the acetic anhydride catalysis method according to claim 7, it is characterized in that piece-rate system comprises the hydrogenation apparatus of common one or more levels cooling device and many chlorine product.
9. the gained solid strong acid prepares in the chloroacetic technique as the application of co-catalyst at the acetic anhydride catalysis method according to claim 7, it is characterized in that the liquid outlet of each reactor is provided with corrosion resistant network of micropores envelope.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04210241A (en) * | 1990-12-04 | 1992-07-31 | Toyota Motor Corp | Catalyst for cleaning exhaust gas |
| CN1298860A (en) * | 1999-12-08 | 2001-06-13 | 重庆嘉陵化学制品有限公司 | Process for preparing chloracetic acid by continuous chlorination and its equipment |
| CN1680251A (en) * | 2005-01-29 | 2005-10-12 | 太原理工大学 | Synthesis of chloroacetic acid |
-
2013
- 2013-07-15 CN CN2013102954683A patent/CN103357426A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04210241A (en) * | 1990-12-04 | 1992-07-31 | Toyota Motor Corp | Catalyst for cleaning exhaust gas |
| CN1298860A (en) * | 1999-12-08 | 2001-06-13 | 重庆嘉陵化学制品有限公司 | Process for preparing chloracetic acid by continuous chlorination and its equipment |
| CN1680251A (en) * | 2005-01-29 | 2005-10-12 | 太原理工大学 | Synthesis of chloroacetic acid |
Non-Patent Citations (1)
| Title |
|---|
| 方建华等: "SO42-/TiO2-ZrO2固体酸催化剂催化废弃动植物油脂制备生物柴油", 《化学与生物工程》, vol. 28, no. 10, 31 December 2011 (2011-12-31), pages 1 - 2 * |
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Application publication date: 20131023 |