CN104447169A - Method for preparing vinyl acetylene by employing ultrasonic enhanced acetylene dimer - Google Patents
Method for preparing vinyl acetylene by employing ultrasonic enhanced acetylene dimer Download PDFInfo
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- CN104447169A CN104447169A CN201410789637.3A CN201410789637A CN104447169A CN 104447169 A CN104447169 A CN 104447169A CN 201410789637 A CN201410789637 A CN 201410789637A CN 104447169 A CN104447169 A CN 104447169A
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- acetylene
- vinylacetylene
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Abstract
The invention discloses a method for preparing vinyl acetylene by employing ultrasonic enhanced acetylene dimer. The adopted catalyst belongs to a nieuwland catalyst; the ratio of cuprous chloride to ammonium chloride to hydrochloric acid to water is 30.75kg to 15.67kg to 0.3L to 45L; the acetylene dimer reaction process is carried out in a reaction device with an ultrasonic wave; the power of the ultrasonic wave is 120W; the frequency is 40kHz; and the method comprises the following steps: (1) firstly, adding ammonium chloride and water to the reaction device, and introducing nitrogen, so as to stir bubbles during discharging air; (2) adding cuprous chloride and hydrochloric acid to the reaction device, further introducing nitrogen and stirring bubbles; and (3) replacing nitrogen with acetylene, further stirring bubbles, and starting the ultrasonic wave device, so as to prepare the vinyl acetylene in a manner of enhancing the acetylene dimer reaction. Compared with the prior art, the selectivity of the vinyl acetylene disclosed by the invention is greatly improved; the conversion rate per pass of the acetylene and the single pass yield of the vinyl acetylene are improved to different extents; and in a word, the comprehensive benefits of the method are relatively high.
Description
Technical field
The present invention relates to acetylene dimer reaction process and prepare the method for vinylacetylene.
Background technology
Chloroprene rubber is elastomeric important kind, has a wide range of applications in the industry.Chloroprene rubber is polymerized by monomer chloroprene, and producing the method for chloroprene one of main is carbide acetylene method.Its process first prepares vinylacetylene by acetylene dimer, then obtain monomer chloroprene with vinylacetylene and hydrochloric acid reaction.Preparing in the process of vinylacetylene by acetylene dimer, the activity and selectivity of catalyzer is crucial.Traditional acetylene dimerization catalyst is Nieuland catalyst, and this catalyzer is by cuprous chloride (Cu
2c1
2), ammonium chloride (NH
4cl) and hydrochloric acid (HCl) by a certain amount of formulated aqueous solution.This catalyzer is continued to use for many years because having the preparation advantage such as simple, with low cost in the industry, but still also exist that by product is more, the yield of vinylacetylene and the shortcoming such as selectivity is low, the oily particulate state superpolymer particularly produced in production process, it has that specific surface area is large, high adsorption capacity, easily emulsification, cause separation difficulty, in catalyst regeneration process, often adopt physical sepn, catalyzer enters in waste with superpolymer, causes effective catalyst to lose in a large number.In addition, catalyzer can also enter superpolymer inside, make catalyzer can not with acetylene into contact, make acetylene dimer reaction efficiency low.Therefore, Chinese scholars input great effort is studied.This technology is through improving for many years, and product yield is improved, but also there is larger room for improvement.For improving acetylene per pass conversion and vinylacetylene once through yield, Authorization Notice No. is CN102267856B, name is called the patent of invention of " method of preparing vinyl acetylene through electric-field-enhanced dimerization of acetylene ", improve for aqueous systems Nieuland catalyst catalyzing acetylene dimerization, the method has mainly been aided with electric field in the whole reaction process of acetylene dimer, by electric field-enhanced acetylene dimer, acetylene per pass conversion and vinylacetylene once through yield are all increased.But the vinylacetylene selectivity of the method is but still lower.
Summary of the invention
The object of this invention is to provide the method that the higher intensified by ultrasonic wave acetylene dimer of a kind of vinylacetylene selectivity prepares vinylacetylene.
For realizing described object, provide a kind of like this intensified by ultrasonic wave acetylene dimer to prepare the method for vinylacetylene, aspect same as the prior art is, the catalyzer that the method adopts is by the formulated aqueous solution of cuprous chloride, ammonium chloride and hydrochloric acid.Its improvements are, the component proportion of described catalyzer is, cuprous chloride: ammonium chloride: hydrochloric acid: water=30.75kg: 15.67kg: 0.3L: 45L; Described acetylene dimer reaction process is carried out being added with in hyperacoustic reaction unit;
Wherein, the mass percent concentration of hydrochloric acid is 37 ~ 38%; Hyperacoustic power is 120W, frequency is 40kHz; The step of the method is as follows:
(1) under constant temperature, first in reaction unit, add ammonium chloride and water according to described proportioning, then pass into nitrogen with excluding air while, bubbling stirs to make ammonium chloride fully dissolve;
(2) in reaction unit, add cuprous chloride and hydrochloric acid again according to described proportioning, then continue to pass into nitrogen with while excluding air, bubbling stirs to make cuprous chloride also fully dissolve;
(3) after catalyzer each component fully mixes, substitute nitrogen with acetylene, and continue bubbling stirring; Meanwhile, start ultrasonic unit, to strengthen the mode of acetylene dimer reaction to prepare vinylacetylene; After product ethylene ethyl-acetylene is without obvious increasing, stopped reaction.
As can be seen from scheme, the present invention is coming in the process of catalyzing acetylene dimerization for aqueous systems Nieuland catalyst, the strengthening means not only adopted completely different from prior art (of the present invention is the intensified by ultrasonic wave being different from prior art), but also correspondingly have adjusted the proportioning of Nieuland catalyst component.So, just make use of hyperacoustic cavatition and high frequency oscillation effect fully, accelerate acetylene dimer reaction.Checking shows, adopts the vinylacetylene selectivity ratios after the inventive method to adopt the much higher of electric field-enhanced prior art.It will be apparent to those skilled in that, the ability of to be acetylene conversion the be principal product vinylacetylene of vinylacetylene selectivity reflection, the higher explanation acetylene conversion of vinylacetylene selectivity is principal product vinylacetylene (CH
2=CH-C ≡ CH) ability stronger.Result so also illustrate that and invention also improves acetylene per pass conversion; Equally also illustrate that vinylacetylene once through yield has had further lifting.Those skilled in the art is clear equally, is preparing in the process of vinylacetylene by acetylene dimer, and vinylacetylene can with acetylene further combined with generating superpolymer.And after with intensified by ultrasonic wave, also having by the electric field-enhanced effect do not had, that is exactly can stop the generation of superpolymer to a certain extent and gather.Thus, just can effectively avoid and crack the parcel of superpolymer to catalyzer, and then obtain the technique effect reducing catalyst loss; Obviously, the situation also simultaneously avoiding superpolymer blocking reaction unit pipeline preferably occurs.In addition, hyperacoustic strengthening effect, is also extremely conducive to the formation speed improving vinylacetylene, also just naturally shortens the residence time of vinylacetylene in reaction unit; And the shortening of this residence time, make again the superpolymer being an impediment to production more be difficult to a large amount of generation.
In brief, compared with prior art, the advantage that comprehensive benefit of the present invention is higher.
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment
Intensified by ultrasonic wave acetylene dimer prepares the method for vinylacetylene, and the catalyzer that the method adopts is by the formulated aqueous solution of cuprous chloride, ammonium chloride and hydrochloric acid.In the present invention, the component proportion of described catalyzer is, cuprous chloride: ammonium chloride: hydrochloric acid: water=30.75kg: 15.67kg: 0.3L: 45L; Described acetylene dimer reaction process is carried out being added with in hyperacoustic reaction unit;
Wherein, the mass percent concentration of hydrochloric acid is 37 ~ 38%; Hyperacoustic power is 120W, frequency is 40kHz; The step of the method is as follows:
(1) under constant temperature, first in reaction unit, add ammonium chloride and water according to proportioning, then pass into nitrogen with excluding air while, bubbling stirs to make ammonium chloride fully dissolve;
(2) in reaction unit, add cuprous chloride and hydrochloric acid again according to described proportioning, then continue to pass into nitrogen with while excluding air, bubbling stirs to make cuprous chloride also fully dissolve;
(3) after described catalyzer each component fully mixes, substitute nitrogen with acetylene, and continue bubbling stirring; Meanwhile, start ultrasonic unit, to strengthen the mode of acetylene dimer reaction to prepare vinylacetylene; After product ethylene ethyl-acetylene is without obvious increasing, stopped reaction.Because it will be apparent to those skilled in that, whether vinylacetylene, without obviously increase, normally accesses gas chromatograph in reaction unit and carries out detecting and judge, therefore do not describe in detail.
After obtaining product ethylene ethyl-acetylene, product and reactant just can be allowed all to enter absorption tower, to realize being separated of acetylene and vinylacetylene, unreacted acetylene enters bubbling column reactor recycle.Vinylacetylene enters reaction tower and hcl reaction synthesizes Chloroprene monomer.
Further, for more effectively accelerating the generation of vinylacetylene, the temperature of constant temperature described in step (1) is controlled between 75 ~ 85 DEG C better.
Further say, for more effectively improving the productive rate of vinylacetylene, substituting the air speed after nitrogen with described acetylene in step (3) and controlling at 160 ~ 210h
-1between be advisable.
The present invention have passed the experimental verification of comparative, the method described in the prior art document (CN102267856B) that comparison other is quoted as proof in background technology part for this specification sheets.For convincing, select the unidirectional pulse electric current that effect in the prior art is best in electric field-enhanced method, and adopt its working parameter completely.For there being comparability, both catalyst components are all identical with proportioning; All the other are except acetylene air speed is in three comparative group except some difference, and it is identical that all the other contrast verification processes and above-mentioned embodiment are introduced.The result see proof list (all fixed values are not recorded in proof list, in table " current density " refer to prior art adopt unidirectional pulse electric current time current density, corresponding forward current ON time and forward current turn-off time, be 0.5ms in each case.）。
Proof list:
Note: the numerical value during the acetylene per pass conversion in proof list, vinylacetylene once through yield and vinylacetylene selectivity are every, the peak height normalization method of gas-chromatography is all adopted to detect reacted various gas, then, according to acetylene per pass conversion, vinylacetylene once through yield and vinylacetylene optionally formula carry out calculating obtaining.
Special instruction, in the prior art document (CN102267856B) that the present invention quotes as proof in background technology part, do not record the checking situation of vinylacetylene once through yield, its numerical value obtains and records when the present invention is contrast experiment.
As can be seen from the contrast of above-mentioned proof list, use intensified by ultrasonic wave acetylene dimer of the present invention to prepare the method for vinylacetylene, relative to prior art, its vinylacetylene has optionally truly had very large raising.Incident, vinylacetylene once through yield and acetylene per pass conversion there has also been the different raising of degree.Observe in contrast experiment's process, also can know and find that the superpolymer growing amount of the inventive method is obviously less than prior art.
Claims (3)
1. intensified by ultrasonic wave acetylene dimer prepares the method for vinylacetylene, the catalyzer that the method adopts is by the formulated aqueous solution of cuprous chloride, ammonium chloride and hydrochloric acid, it is characterized in that, the component proportion of described catalyzer is, cuprous chloride: ammonium chloride: hydrochloric acid: water=30.75kg: 15.67kg: 0.3L: 45L; Described acetylene dimer reaction process is carried out being added with in hyperacoustic reaction unit;
Wherein, the mass percent concentration of described hydrochloric acid is 37 ~ 38%; Described hyperacoustic power is 120W, frequency is 40kHz; The step of the method is as follows:
(1) under constant temperature, first in reaction unit, add ammonium chloride and water according to described proportioning, then pass into nitrogen with excluding air while, bubbling stirs to make ammonium chloride fully dissolve;
(2) in reaction unit, add cuprous chloride and hydrochloric acid again according to described proportioning, then continue to pass into nitrogen with while excluding air, bubbling stirs to make cuprous chloride also fully dissolve;
(3) after described catalyzer each component fully mixes, substitute nitrogen with acetylene, and continue bubbling stirring; Meanwhile, start ultrasonic unit, to strengthen the mode of acetylene dimer reaction to prepare vinylacetylene; After product ethylene ethyl-acetylene is without obvious increasing, stopped reaction.
2. intensified by ultrasonic wave acetylene dimer prepares the method for vinylacetylene according to claim 1, it is characterized in that, described in step (1), the temperature of constant temperature is 75 ~ 85 DEG C.
3. according to claim 1 or 2, intensified by ultrasonic wave acetylene dimer prepares the method for vinylacetylene, it is characterized in that, substitutes the air speed after nitrogen in step (3) control at 160 ~ 210h with described acetylene
-1between.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410789637.3A CN104447169A (en) | 2014-12-19 | 2014-12-19 | Method for preparing vinyl acetylene by employing ultrasonic enhanced acetylene dimer |
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|---|---|---|---|
| CN201410789637.3A CN104447169A (en) | 2014-12-19 | 2014-12-19 | Method for preparing vinyl acetylene by employing ultrasonic enhanced acetylene dimer |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575388A (en) * | 2009-06-10 | 2009-11-11 | 重庆大学 | Method for separating catalyst from associated polymer |
| CN101786022A (en) * | 2010-03-17 | 2010-07-28 | 重庆大学 | Catalyst for preparing vinyl acetylene and application method thereof |
| CN102267856A (en) * | 2011-08-09 | 2011-12-07 | 重庆大学 | Method for preparing vinyl acetylene through electric-field-enhanced dimerization of acetylene |
| CN102580630A (en) * | 2012-01-09 | 2012-07-18 | 重庆大学 | Bubble tower reactor for enhancing acetylene dimerization |
| CN102731241A (en) * | 2012-07-04 | 2012-10-17 | 重庆大学 | Method for synthesizing vinylacetylene by water system |
| CN102775266A (en) * | 2012-03-20 | 2012-11-14 | 重庆大学 | Method for synthesizing vinylacetylene through acetylene dimerization |
-
2014
- 2014-12-19 CN CN201410789637.3A patent/CN104447169A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575388A (en) * | 2009-06-10 | 2009-11-11 | 重庆大学 | Method for separating catalyst from associated polymer |
| CN101786022A (en) * | 2010-03-17 | 2010-07-28 | 重庆大学 | Catalyst for preparing vinyl acetylene and application method thereof |
| CN102267856A (en) * | 2011-08-09 | 2011-12-07 | 重庆大学 | Method for preparing vinyl acetylene through electric-field-enhanced dimerization of acetylene |
| CN102580630A (en) * | 2012-01-09 | 2012-07-18 | 重庆大学 | Bubble tower reactor for enhancing acetylene dimerization |
| CN102775266A (en) * | 2012-03-20 | 2012-11-14 | 重庆大学 | Method for synthesizing vinylacetylene through acetylene dimerization |
| CN102731241A (en) * | 2012-07-04 | 2012-10-17 | 重庆大学 | Method for synthesizing vinylacetylene by water system |
Non-Patent Citations (2)
| Title |
|---|
| A.M.津斯特林格: "《超声波在化工过程中的应用》", 31 October 1963, 中国工业出版社 * |
| 侯文顺: "《高聚物生产技术》", 31 January 2003, 化学工业出版社 * |
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Application publication date: 20150325 |