CN103012320B - Method for preparing 1,2-epoxybutane - Google Patents
Method for preparing 1,2-epoxybutane Download PDFInfo
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- CN103012320B CN103012320B CN201110290123.XA CN201110290123A CN103012320B CN 103012320 B CN103012320 B CN 103012320B CN 201110290123 A CN201110290123 A CN 201110290123A CN 103012320 B CN103012320 B CN 103012320B
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Abstract
The invention discloses a method for preparing 1,2-epoxybutane, comprising the following step of enabling butane to contact an oxidizing agent under the oxidation reaction condition. The method is characterized in that the oxidizing agent is a gas containing ozone. The method has the advantages that the selectivity of prepared epoxybutane is high and effective utilization of ozone is high.
Description
Technical field
The invention relates to a kind of method that butylene oxidation prepares 1,2-butylene oxide ring.
Background technology
Oxybutylene (BO), also known as 1,2-butylene oxide ring, is a kind of important Organic Chemicals.There is extensive use, such as, can butyleneglycol be produced, butanolamines etc., can also replace the thinner that acetone does pyroxylin(e)finish, also can be used as the oxidation inhibitor of chlorine-containing compound, produce the corrosion inhibitor of vinyl chloride resin, tensio-active agent, gasoline dope, the stablizer etc. of chlorinated solvent.
Current industrial production oxybutylene mainly adopts chlorohydrination, namely first makes 1-butylene chlorohydrination with hypochlorous acid, and then epoxidation.But the method uses poisonous chlorine, seriously corroded also produces the chlorine-contained wastewater, waste residue etc. of a large amount of contaminate environment, and do not meet the requirement of Green Chemistry and cleaner production, therefore along with the raising day by day of environmental protection requirement, this technique will finally be eliminated.
In recent years, the method for 1-butylene Direct Epoxidation generation oxybutylene under catalyst action causes the common concern of people.By contrast, 1-butylene Direct Epoxidation method eliminates this procedure of chlorohydrination, thus simplifies Production Flow Chart, particularly without chlorine, greatly reduces environmental pollution.If " fine-chemical intermediate " is in April, 2003 " titanium molecular sieve catalysis synthesis 1,2-butylene oxide ring " disclose the epoxidation of 1-butylene on titanium-silicon molecular sieve catalyst in a literary composition, also the method for a kind of synthesis 1,2-butylene oxide ring is disclosed in CN101085763A.Problems existing all uses hydrogen peroxide as oxidant, and due to hydrogen peroxide extremely unstable, heat, light, uneven surface, heavy metal and other impurity can decompose, and have corrodibility, will take special security measures in packaging, storage, transport.Be subject to the limitation of cost and safety problem, and prepare hydrogen peroxide and need independent equipment and the recycle system, cost is comparatively large, and before not have stricter environmental regulation appearance, this liquid phase process industrialization has certain economic obstacle.
Summary of the invention
The object of this invention is to provide a kind of technique simple, butylene oxidation method with low cost, 1,2-butylene oxide ring selectivity is good.
1 is prepared in order to overcome prior art, the problems referred to above that 2-butylene oxide ring method exists, the present inventor conducts in-depth research, find: adopt ozone to carry out oxybutylene as oxygenant, can overcome on the one hand that the operational condition that prior art exists is harsh, equipment corrosion is serious and the defect of contaminate environment, and gratifying 1,2-butylene oxide ring selectivity can be obtained, this completes the present invention.
The invention provides a kind of method of butylene oxidation, the method comprises, and under oxidation reaction condition, by butylene and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
The method of butylene oxidation provided by the invention, oxygenant is made with ozone, can obtain high butylene oxide ring selectivity and comparatively high ozone effective rate of utilization in unstripped gas without the need to adding any initiator, the method process is simple and easy to control, is beneficial to suitability for industrialized production and application.
Embodiment
Provided by the invention 1, the preparation method of 2 butylene oxide rings, the method comprises, and under oxidation reaction condition, by butylene and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
According to method of the present invention, adopt the gas containing ozone as oxygenant.(molecular formula is O to ozone
3, have another name called three atomic oxygens, be commonly called as " good fortune oxygen, super oxygen, oxygen of living ") at normal temperatures and pressures, for being nattier blue gas.The present inventor finds in research process, and adopt the gas containing ozone to carry out oxybutylene as oxygenant, for 1,2 butylene oxide rings have higher selectivity, and its simple process is easy, and operational condition is gentle.Further, ozone can disintegrate be oxygen at normal temperatures, can not produce and such as use hydrogen peroxide to carry out the shortcoming such as processing to the solution containing hydrogen peroxide as the needs faced during oxygenant.Therefore, according to the inventive method environmental friendliness.
According to method of the present invention, the described gas containing ozone can be ozone, can also be the mixed gas of ozone and diluent gas.According to method of the present invention, the described gas containing ozone is preferably the mixed gas of ozone and diluent gas, can regulate easily like this, thus control speed of reaction better to the concentration of ozone.
In the present invention, when the described gas containing ozone is the mixed gas of ozone and diluent gas, in described mixed gas, the concentration of ozone can carry out appropriate selection according to concrete oxidation reaction condition.Preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %.More preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %.Usually, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone can be 5-80 volume %, is preferably 5-50 volume %, is more preferably 5-20 volume %.
The present invention is not particularly limited for the kind of described diluent gas, and described diluent gas can be such as at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.Preferably, described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.According to the present invention, ozone can be mixed with above-mentioned diluent gas, thus the described mixed gas containing ozone of preparation; Because air contains oxygen, carbonic acid gas and nitrogen, also by ozone and air mixed, thus the mixed gas of ozone described in preparation, can be contained.According to method of the present invention, when adopting the on-the-spot generation ozone of ozonizer, oxygen can be adopted as the source of oxygen of described ozonizer, air also can be adopted to provide oxygen to described ozonizer.The smelly oxygen purity adopting oxygen to obtain as the source of oxygen of described ozonizer is higher, can obtain higher butene conversion, 1,2-butylene oxide ring selectivity; Adopt air as the source of oxygen of described ozonizer, then can reduce running cost further.
According to method of the present invention, at the mixed gas that described oxygenant is ozone and diluent gas, and described diluent gas is when being two or more, the present invention is not particularly limited for the content of each diluent gas, as long as final contains in the gas of ozone, the content of ozone can by butylene oxidation, such as: the content of described ozone can be ozone content mentioned above.
One according to the present invention preferred embodiment in, the described gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.One according to the present invention more preferred embodiment in, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
Method according to the present invention realizes the operational condition with gentleness containing the gas of ozone as oxygenant and higher selectivity prepares 1 by adopting, 2 butylene oxide rings, also can not produce the object of serious corrosion to equipment simultaneously, the present invention without particular requirement, can carry out appropriate selection according to concrete application scenario for the mol ratio of the ozone in butylene and oxygenant.Guaranteeing the transformation efficiency and 1 of butylene, under the optionally condition of 2-butylene oxide ring, from the consumption reducing ozone further, and then reduction is set out according to the angle of the cost of method of the present invention further, the mol ratio of the ozone in described butylene and oxygenant is preferably 1: 0.1-10, be more preferably 1: 0.1-5, more preferably 1: 0.5-5.
According to method of the present invention, the contact of butylene and oxygenant is preferably carried out in the presence of a titanium-containing catalyst.The present inventor finds in research process, when carrying out under existence at titanium-containing catalyst of the contact of butylene and oxygenant, the transformation efficiency of the butylene of the inventive method and the selectivity of 1,2-butylene oxide ring can be improved, particularly can increase substantially the effective rate of utilization of ozone.
According to method of the present invention, the consumption of described titanium-containing catalyst can carry out appropriate selection according to concrete application scenario.Preferably, in titanium dioxide, the mol ratio of described titanium-containing catalyst and butylene is 1: 0.1-1000.More preferably, in titanium dioxide, the mol ratio of described titanium-containing catalyst and butylene is 1: 1-500.
According to method of the present invention, described titanium-containing catalyst can be various forms of titanium-containing catalyst.Preferably, described titanium-containing catalyst is at least one in molecular sieve containing titanium, the preformed catalyst of molecular sieve containing titanium, amorphous silicon titanium and titanium dioxide.More preferably, described titanium-containing catalyst is at least one in the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS (as Ti-MCM-41, Ti-SBA-15) of hexagonal structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS (as Ti-ZSM-48) of other structures and titanium dioxide.More preferably, described titanium-containing catalyst is the HTS (as TS-1) of MFI structure.Above-mentioned molecular sieve can be commercially available, or adopts method well known in the art to synthesize, and repeats no more herein.
According to method of the present invention, described titanium-containing catalyst most preferably is the MFI structure HTS of hollow structure crystal grain, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Hereinafter, the HTS of the type is called hollow HTS.
According to method of the present invention, the contact of butylene and oxygenant is preferably carried out in the presence of solvent, the contact of butylene and oxygenant can be made so more even, thus better control speed of response.The present invention is not particularly limited for the kind of described solvent, all kinds of SOLVENTS that described solvent can be commonly used for this area.Preferably, described solvent is water, C
1-C
10alcohol, C
3-C
10ketone, C
2-C
8nitrile and C
1-C
6carboxylic acid at least one.Such as, described solvent can be at least one in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile and acetic acid.The present inventor finds unexpectedly in research process, is water and/or C at described solvent
3-C
8ketone time, the transformation efficiency of butylene and the selectivity of 1,2-butylene oxide ring can be improved further.Further preferably, described solvent is water, butanone and/or acetone.
According to method of the present invention, the amount of described solvent can be the routine selection of this area.From the angle of cost reducing further method of the present invention, the mol ratio of described butylene and solvent is preferably 1: 1-150, is more preferably 1: 1-100, and more preferably 1: 1-50.
According to method of the present invention, for described oxidation reaction condition without particular requirement, it can be conventional oxidation reaction condition.Under preferable case, described oxidation reaction condition comprises: temperature can be 0-180 DEG C, is preferably 20-160 DEG C, more preferably 20-120 DEG C; Pressure can be 0.1-3MPa, is preferably 0.1-2.5MPa, more preferably 0.1-2MPa.According to method of the present invention, the duration of contact of butylene and oxygenant can carry out appropriate selection.Usually, the time of described contact can be 0.1-10 hour, is preferably 1-5 hour.It should be noted that, when at said temperatures, when can produce required pressure, described pressure can be autogenous pressure, when at said temperatures, when the pressure that described temperature produces does not reach required pressure, described pressure can apply pressure to realize by the external world, this is technology well known in the art, no longer describes in detail herein.
According to method of the present invention, ordinary method can be adopted to be separated from the product of contact of butylene and oxygenant by 1,2-butylene oxide ring.Such as: by described product of contact is carried out fractionation, thus 1,2-butylene oxide ring can be isolated.The method of described fractionation and condition are known in the field, repeat no more herein.
According to method of the present invention, can adopt periodical operation, also can adopt operate continuously etc., feed way also can be any suitable mode well known by persons skilled in the art, and the present invention, does not repeat at this all without particular requirement one by one to this.During operate continuously, be 10-10000h in ozone air speed
-1react under condition, ozone air speed is preferably 10-5000h
-1.
The invention will be further described for following embodiment, but therefore do not limit content of the present invention.
In embodiment and comparative example, if not otherwise specified, used reagent is commercially available analytical reagent, and used reactor is universal 250mL stainless steel autoclave formula reactor.
Ozone used provides for the NLO-15 type ozonizer produced by Fujian New Continent Environmental Protection Technology Co., Ltd, and ozone concn is adjustable, and maximum volume concentration can reach 80%.In following examples if not otherwise specified, source of oxygen is all used to prepare ozone.
In embodiment, HTS (TS-1) catalyzer used is by document [Zeolites, 1992, Vol.12 943-950 page] described in (TS-1) sieve sample of preparing of method, titanium oxide content is 2.5 % by weight.
In embodiment, the Industrial products of HTS described in hollow HTS HTS system CN1301599A used (build feldspathization stock company and manufacture by Hunan, be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180 nanometer; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index such as the transformation efficiency of reactant and the selectivity of product on this basis.
In embodiment and comparative example:
Embodiment 1
Under be 60 DEG C and pressure being 0.5MPa in temperature, be oxygenant with ozone (15% volume ratio, all the other are oxygen), by butylene, ozone and solvent acetone according to 1: 1: 1 mol ratio react.
The result of reacting 2 hours is as follows: butene conversion is 36%; Butylene oxide ring selectivity is 79%; Ozone effective rate of utilization is 52%.
Embodiment 2
Under be 20 DEG C and pressure being 1.5MPa in temperature, be oxygenant with ozone (30% volume ratio, all the other are air), by butylene, ozone and solvent acetone according to 1: 1: 5 mol ratio react.
The result of reacting 5 hours is as follows: butene conversion is 32%; Butylene oxide ring selectivity is 82%; Ozone effective rate of utilization is 55%.
Embodiment 3
Under be 80 DEG C and pressure being 0.2MPa in temperature, be oxygenant with ozone (5% volume ratio, all the other are oxygen), by butylene, ozone and solvent acetonitrile according to 1: 2: 10 mol ratio react.
The result of reacting 2 hours is as follows: butene conversion is 41%; Butylene oxide ring selectivity is 73%; Ozone effective rate of utilization 51%.
Embodiment 4
Under be 40 DEG C and pressure being 0.1MPa in temperature, be oxygenant with ozone (15% volume ratio, all the other are oxygen), by butylene, ozone and solvent acetone according to 1: 4: 50 mol ratio react.
The result of reacting 3 hours is as follows: butene conversion is 40%; Butylene oxide ring selectivity is 81%; Ozone effective rate of utilization is 56%.
Embodiment 5
The present embodiment illustrates reaction process in the presence of a catalyst and result.
Take TS-1 as catalyzer, the molar ratio of catalyzer and butylene is 1: 50, and ozone volume space velocity is 25h
-1, other reaction conditions is with embodiment 4.
The result of reacting 3 hours is as follows: butene conversion is 46%; Butylene oxide ring selectivity is 89%; Ozone effective rate of utilization is 76%.
Embodiment 6
Under be 50 DEG C and pressure being 1.0MPa in temperature, be oxygenant with ozone (10% volume ratio, all the other are air), by butylene, ozone and aqueous solvent according to 1: 0.3: 3 mol ratio react.
The result of reacting 4 hours is as follows: butene conversion is 21%; Butylene oxide ring selectivity is 79%; Ozone effective rate of utilization is 52%.
Embodiment 7
Under temperature is 120 DEG C and pressure is 1.0MPa, is oxygenant with ozone (10% volume ratio, all the other are carbon dioxide and oxygen), butylene, ozone and solvent acetone are reacted according under the mol ratio of 1: 0.6: 25.
The result of reacting 3 hours is as follows: butene conversion is 38%; Butylene oxide ring selectivity is 80%; Ozone effective rate of utilization is 57%.
Embodiment 8
The present embodiment illustrates reaction process in the presence of a catalyst and result.
With TiO
2for catalyzer (commercially available, Detitanium-ore-type), the molar ratio of catalyzer and butylene is 1: 5, and ozone volume space velocity is 5000h
-1, other reaction conditions is with embodiment 7.
The result of reacting 3 hours is as follows: butene conversion is 56%; Butylene oxide ring selectivity is 83%; Ozone effective rate of utilization is 80%.
Embodiment 9
Identical with the method for embodiment 5, replaced by HTS unlike TS-1, react 3 hours: butene conversion is 51%; Butylene oxide ring selectivity is 86%; Ozone effective rate of utilization is 78%.
Embodiment 10
Identical with the method for embodiment 5, unlike, TS-1 by Ti-MCM-41 (according to prior art Corma etc. at Chem.Commun., 1994, method preparation described in 147-148, titanium oxide content is 3 % by weight) replace, react 3 hours: butene conversion is 34%; Butylene oxide ring selectivity is 73%; Ozone effective rate of utilization is 70%.
Embodiment 11
Identical with the method for embodiment 5, unlike, TS-1 by Ti-Beta (according to prior art Takashi Tatsumi etc. at J.Chem.Soc.Chem.Commun.1997, method preparation described in 677-678, titanium oxide content is 2.6 % by weight) replace, the molar ratio of catalyzer and butylene changes 1: 500 into, reacts 3 hours: butene conversion is 39%; Butylene oxide ring selectivity is 78%; Ozone effective rate of utilization is 67%.
Embodiment 12
Identical with the method for embodiment 5, unlike, TS-1 is by TiO
2(Beijing chemical reagents corporation, Detitanium-ore-type) replaces, and reacts 3 hours: butene conversion is 36%; Butylene oxide ring selectivity is 81%; Ozone effective rate of utilization is 82%.
Embodiment 13
Identical with the method for embodiment 5, unlike, solvent is acetic acid, reacts 3 hours: butene conversion is 66%; Butylene oxide ring selectivity is 68%; Ozone effective rate of utilization is 68%.
Embodiment 14
Identical with the method for embodiment 1, be ethanol unlike solvent, react 3 hours: butene conversion is 35%; Butylene oxide ring selectivity is 82%; Ozone effective rate of utilization is 71%.
Embodiment 15
Identical with the method for embodiment 14, unlike, do not carry out in the presence of solvent, react 3 hours: butene conversion is 9%; Butylene oxide ring selectivity is 39%; Ozone effective rate of utilization is 36%.
Comparative example 1
The method identical with embodiment 5 is adopted to prepare 1,2-butylene oxide ring, unlike, use oxygen as oxygenant.React 3 hours: butene conversion is 6%; Butylene oxide ring selectivity is 3%.
Comparative example 2
The method identical with embodiment 8 is adopted to prepare 1,2-butylene oxide ring, unlike, use oxygen as oxygenant.React 3 hours: butene conversion is 5%; Butylene oxide ring selectivity is 1%.
Claims (8)
1. the preparation method of a 2-butylene oxide ring, the method comprises, under oxidation reaction condition, by butylene and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone, described contact is carried out in the presence of a titanium-containing catalyst, and in titanium dioxide, the mol ratio of described titanium-containing catalyst and butylene is 1: 0.1-1000, wherein, described titanium-containing catalyst is the HTS of MFI structure, the HTS of MEL structure, the HTS of BEA structure, the HTS of MWW structure, the HTS of MOR structure, the HTS of TUN structure, at least one in the two dimension HTS of hexagonal structure and titanium dioxide.
2., according to the process of claim 1 wherein, the mol ratio of the ozone in described butylene and oxygenant is 1: 0.1-10.
3. according to the method for claim 1, wherein, the said gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.
4. according to the method for claim 3, wherein, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
5., according to the process of claim 1 wherein, the HTS of described MFI structure, crystal grain is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
6. according to the method for any one in claim 1-4, wherein, described contact is carried out in the presence of solvent, and described solvent is at least one in water, ethanol, acetone, acetonitrile and acetic acid, and the mol ratio of described butylene and solvent is 1: 1-150.
7. according to the method for any one in claim 1-4, wherein, described oxidation reaction condition comprises: temperature is 0-180 DEG C, and pressure is 0.1-3MPa, and the time is 0.1-10 hour.
8. according to the method for claim 7, wherein, described temperature is 20-160 DEG C, and pressure is 0.3-2.5MPa.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643459A (en) * | 2008-08-07 | 2010-02-10 | 中国石油化工股份有限公司 | Method for preparing 1,2-butylene oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643459A (en) * | 2008-08-07 | 2010-02-10 | 中国石油化工股份有限公司 | Method for preparing 1,2-butylene oxide |
Non-Patent Citations (3)
| Title |
|---|
| 以C_4烃为原料制备环氧丁烷;曹魁等;《大连交通大学学报》;20080615;第29卷(第03期);第64-66页 * |
| 钛硅分子筛催化1-丁烯环氧化研究;马书启等;《燃料化学学报》;20050825;第33卷(第04期);第509-512页 * |
| 钛硅分子筛催化合成1,2-环氧丁烷;王军民等;《精细化工中间体》;20030430;第33卷(第2期);第11-13页 * |
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