CN1286808C - Process for preparing tert-butyl hydroperoxide - Google Patents
Process for preparing tert-butyl hydroperoxide Download PDFInfo
- Publication number
- CN1286808C CN1286808C CN 200410038310 CN200410038310A CN1286808C CN 1286808 C CN1286808 C CN 1286808C CN 200410038310 CN200410038310 CN 200410038310 CN 200410038310 A CN200410038310 A CN 200410038310A CN 1286808 C CN1286808 C CN 1286808C
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- trimethyl carbinol
- mouthfuls
- reaction
- hts
- 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 - Lifetime
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 88
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- 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 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract 2
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 13
- 238000013019 agitation Methods 0.000 description 10
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical group CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and analytical pure Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing tert-butyl hydrogen peroxide by the catalytic oxidation of tert-butanol. The method comprises the following steps: tert-butanol is in contact with hydrogen peroxide for 0.5 to 10 hours according to a mol ratio of 0.5 to 10 at 40 to 100 DEG C in the presence of titanium-silicon molecular sieves; every milliliter of reaction solutions can contain 0.005 to 0.1g of titanium-silicon molecular sieves. The disadvantages of device corrosion and harmful discharge caused by traditional catalytic methods of sulphuric acid are overcome by the method, and the problem of difficult separation of the same phases of a reaction solution and a catalyst is solved. In addition, the present invention has the advantages of high selectivity of target products, no by-products, high utilization rate of hydrogen peroxide, high activity and stability of catalysts, and regenerative cycle and use; hydrogen peroxide is converted into water after oxidation reaction, and the method has no pollution to environment.
Description
Technical field
The invention relates to the preparation method of tertbutyl peroxide.More particularly, be about making catalyzer with HTS, being the method for feedstock production tertbutyl peroxide with the trimethyl carbinol.
Background technology
(English name is tertiary butyl hydroperoxide to tertbutyl peroxide, be called for short TBHP), be mainly used in vinyl monomer polymerization starter, thermosetting polyester resin class solidifying agent, also can be used to make ditertiary butyl peroxide, the latter can be used to improve diesel-fuel cetane number.
According to the literature, TBHP is made through liquid phase reaction by Trimethylmethane and oxygen, and the product of Sheng Chenging also has the trimethyl carbinol (US2,845,461, US3,478 simultaneously, 108, US3,816,540, US3,907,902, US4,404,406, US4,408,081, US5,196,597 or the like).
According to another (on " Hangzhou chemical industry " the 2nd phase of nineteen ninety 33-37 page or leaf＜and the Application and Development of the trimethyl carbinol〉literary composition introduces, and the Industrial products tertbutyl peroxide is that catalyzer, hydrogen peroxide are that oxygenant, the catalyzed oxidation trimethyl carbinol obtain with sulfuric acid.Undoubtedly, this technology exists equipment corrosion and environmental pollution problem, and can produce by product, influenced economic benefit.In addition, this technology also exists reaction solution and the not segregative problem of catalyzer homophase.
In addition, do not see other the processing method report of producing TBHP.
Summary of the invention
The method that the purpose of this invention is to provide a kind of new synthesizing tertiary butyl hydrogen peroxide is to solve the problems that exist in the commercial run.
The method of catalyzed oxidation trimethyl carbinol synthesizing tertiary butyl hydrogen peroxide provided by the invention is a catalyzer with the HTS, be that oxygenant carries out catalytic oxidation with the hydrogen peroxide.Specifically, method provided by the invention is: make the trimethyl carbinol and hydrogen peroxide according to 0.5～10, preferred 1～6 mol ratio in the presence of the HTS, under 40～100 ℃, preferred 40～90 ℃, contact 0.5～10 hour, the consumption of HTS should make 0.005～0.1g molecular sieve in every milliliter of reaction solution.
Method provided by the invention is not particularly limited the raw material trimethyl carbinol, and analytical pure, chemical pure, technical pure all can.
Method provided by the invention also is not particularly limited used oxidants hydrogen peroxide, any concentration all can, but consider that from economical and practical angle its concentration is preferably in more than the 25 weight %.
The HTS that method provided by the invention is suitable for can synthesize according to any prior art, but preferably according to disclosed method synthetic among the CN1132699C.
The method of new synthesizing tertiary butyl hydrogen peroxide provided by the invention, equipment corrosion, noxious emission that traditional sulfuric acid catalysis method is brought have not only been overcome, avoided the not segregative problem of reaction solution and catalyzer homophase, and the inventive method purpose product selectivity height, no coupling product; Hydrogen peroxide utilization ratio height; Catalyst activity, stability height, renewable recycling; Hydrogen peroxide carries out becoming water, environmentally safe after the oxidizing reaction, has better industrial application prospect.
Embodiment
Following example will illustrate further to the present invention, but not thereby limiting the invention.
Employed HTS is according to disclosed method synthetic among the CN1132699C among the embodiment, is refinery, China Petrochemical Industry Chang Ling Industrial products, and trade names are the HTS HTS.
The employed trimethyl carbinol is an analytical pure among the embodiment, and chemical reagent six factories in Tianjin produce, and its purity is greater than 95%; Concentration of hydrogen peroxide is 30%H
2O
2, Beijing Chemical Plant's product.
The concentration of each material of reaction back is carried out quantitative analysis with vapor-phase chromatography among the embodiment.Used chromatographic instrument is the GC3400 type that Beijing Analytical Instrument Factory produces; Analysis condition is: 30m capillary column, carrier gas are that nitrogen, the hydrogen flowing quantity of flow 30ml/min is that 30ml/min, air flow quantity are that 300ml/min, temperature of vaporization chamber are 90 ℃, 60 ℃ of column temperatures, detect 150 ℃ of mouthful temperature.
The transformation efficiency of the utilization ratio of the selectivity of tertbutyl peroxide, hydrogen peroxide, the trimethyl carbinol calculates respectively according to the following equation among the embodiment:
The transformation efficiency of the trimethyl carbinol, mol%=tertbutyl peroxide content, mol%
The utilization ratio of hydrogen peroxide, %=trimethyl carbinol transformation efficiency * (trimethyl carbinol and H
2O
2Molar ratio)
Embodiment 1
Take by weighing the 3.5g HTS and be loaded in three mouthfuls of vials of 100ml, add the 50.6ml trimethyl carbinol and 10ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 5.57.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 65 ℃, reacts after 6 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 83.6%, and the transformation efficiency of the trimethyl carbinol is 15.01%.
Embodiment 2
Take by weighing the 4g HTS and be loaded in three mouthfuls of vials of 100ml, add the 27.6ml trimethyl carbinol and 30ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 1.00.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 70 ℃, reacts after 10 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 66.83%, and the transformation efficiency of the trimethyl carbinol is 66.83%.
Embodiment 3
Take by weighing the 4g HTS and be loaded in three mouthfuls of vials of 100ml, add the 41.4ml trimethyl carbinol and 15ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 3.01.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 80 ℃, reacts after 3 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 65.78%, and the transformation efficiency of the trimethyl carbinol is 21.85%.
Embodiment 4
Take by weighing the 4g HTS and be loaded in three mouthfuls of vials of 100ml, add the 41.4ml trimethyl carbinol and 15ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 3.01.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 50 ℃, reacts after 3 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 17.96%, and the transformation efficiency of the trimethyl carbinol is 5.97%.
Embodiment 5
Take by weighing the 1g HTS and be loaded in three mouthfuls of vials of 100ml, add the 41.4ml trimethyl carbinol and 15ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 3.01.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 80 ℃, reacts after 2 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 19.76%, and the transformation efficiency of the trimethyl carbinol is 6.56%.
Embodiment 6
Take by weighing the 5g HTS and be loaded in three mouthfuls of vials of 100ml, add the 41.4ml trimethyl carbinol and 15ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 3.01.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 80 ℃, reacts after 2 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 61.27%, and the transformation efficiency of the trimethyl carbinol is 20.36%.
Embodiment 7
Take by weighing the 4g HTS and be loaded in three mouthfuls of vials of 100ml, add the 27.6ml trimethyl carbinol and 30ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 1.00.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 70 ℃, reacts after 3 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 31.55%, and the transformation efficiency of the trimethyl carbinol is 31.55%.
Embodiment 8
Take by weighing the 4g HTS and be loaded in three mouthfuls of vials of 100ml, add the 46ml trimethyl carbinol and 10ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 2.99.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 70 ℃, reacts after 3 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 72.77%, and the transformation efficiency of the trimethyl carbinol is 24.34%.
Embodiment 9
Take by weighing the 4g HTS and be loaded in three mouthfuls of vials of 100ml, add the 41.4ml trimethyl carbinol and 15ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 3.01.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 70 ℃, reacts after 1 hour, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 27.38%, and the transformation efficiency of the trimethyl carbinol is 9.13%.
Embodiment 10
Take by weighing the 0.5g HTS and be loaded in three mouthfuls of vials of 100ml, add the 46ml trimethyl carbinol and 10ml concentration more successively and be 30% hydrogen peroxide in bottle, this moment, the mol ratio of the trimethyl carbinol and hydrogen peroxide was 2.99.Three mouthfuls of vials are put on the temperature control magnetic stirring apparatus, reflux with condensing tube condensation in three mouthfuls of vial tops, start magnetic agitation and add thermal control, begin reaction.Temperature of reaction is controlled at about 70 ℃, reacts after 3 hours, and the selectivity of tertbutyl peroxide is 100%, and the utilization ratio of hydrogen peroxide reaches 9.03%, and the transformation efficiency of the trimethyl carbinol is 3.01%.
Claims (3)
1, a kind of catalyzed oxidation trimethyl carbinol prepares the method for tertbutyl peroxide, be to make the trimethyl carbinol and hydrogen peroxide contact 0.5～10 hour according to 0.5～10 mol ratio in the presence of the HTS, under 40～100 ℃, the consumption of HTS should make 0.005～0.1g molecular sieve in every milliliter of reaction solution.
2, in accordance with the method for claim 1, the mol ratio of the wherein said trimethyl carbinol and hydrogen peroxide consumption is 1～6.
3, in accordance with the method for claim 1, wherein said contact temperature is 40～90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410038310 CN1286808C (en) | 2004-05-19 | 2004-05-19 | Process for preparing tert-butyl hydroperoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410038310 CN1286808C (en) | 2004-05-19 | 2004-05-19 | Process for preparing tert-butyl hydroperoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1699339A CN1699339A (en) | 2005-11-23 |
| CN1286808C true CN1286808C (en) | 2006-11-29 |
Family
ID=35475616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410038310 Expired - Lifetime CN1286808C (en) | 2004-05-19 | 2004-05-19 | Process for preparing tert-butyl hydroperoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1286808C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314583B (en) * | 2007-05-31 | 2012-05-09 | 中国石油化工股份有限公司 | Method for catalytic oxidation of tert-butanol |
| CN102757374B (en) * | 2011-04-29 | 2014-03-12 | 中国石油化工股份有限公司 | Oxidation method for tert-butyl alcohol |
| CN102863368B (en) * | 2011-07-05 | 2014-08-20 | 中国石油化工股份有限公司 | Method for oxidizing tertiary butanol |
| CN103204792B (en) * | 2012-01-13 | 2014-10-29 | 中国石油化工股份有限公司 | Preparation method of tert-butyl hydroperoxide |
| CN105523983A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for tert-butyl alcohol |
| CN106380437B (en) * | 2016-08-23 | 2018-03-20 | 江苏强盛功能化学股份有限公司 | The preparation method of di-t-butyl peroxide |
| CN110128313B (en) * | 2018-02-09 | 2021-04-06 | 中国石油化工股份有限公司 | Process for preparing tert-butyl hydroperoxide |
-
2004
- 2004-05-19 CN CN 200410038310 patent/CN1286808C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1699339A (en) | 2005-11-23 |
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