CN102531852B - Technology for preparing tert-butyl glycerol ethers by utilizing rare earth modified molecular sieve - Google Patents
Technology for preparing tert-butyl glycerol ethers by utilizing rare earth modified molecular sieve Download PDFInfo
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Abstract
The invention discloses a technology for preparing tert-butyl glycerol ethers by utilizing a rare earth modified molecular sieve. The technology is characterized in that soluble salt containing lanthanum, cerium, neodymium, europium, samarium and praseodymium is adopted to prepare a rare earth salt solution; an H Beta molecular sieve performs ion exchange in the rare earth salt solution through micro-wave heating stirring or conventional heating stirring; and rare earth modified H Beta molecular sieve catalytic agents are obtained after filtration, drying and calcination are carried out. Glycerol and isobutene are taken as raw materials, reactants and rare earth modified Beta molecular sieve catalytic agents are added in a reaction kettle, and a tert-butyl glycerol ether mixture containing mono-tert-butyl glycerol ethers (MTBGs), di-tert-butyl glycerol ethers (DTBG) and tri-tert-butyl glycerol ethers (TTBG) is synthesized under the reaction pressure ranging from 1 to 2Mpa and at the reaction temperature ranging from 50 to 100 DEG C. The technology increases the Bronst acid density of the molecular sieve by utilizing the rare earth modified molecular sieve catalytic agents and adopting an ion-exchange method, and improves the glycerol conversion rate and the tert-butyl glycerol ether selectivity in a glycerol etherification reaction that is catalyzed by adopting the technology.
Description
Technical field
The present invention relates to a kind of glycerine and prepare the method for tertiary butyl glyceryl ether, belong to technical field of organic synthesis.
Background technology
The exploitation of biofuel and commercial applications have developed more than ten years rapidly in Europe and the U.S..It is aspect healthy and environment, and engine flexibility aspect, has the superiority larger than fossil oil.Aspect environment, biofuel is sulfur-bearing not, and obnoxious flavour is (such as suspended particle, NO, CO
2deng) quantity discharged also very low, can effectively reduce the CO that causes Global warming
2life cycle.Aspect the suitability of engine, biofuel has the content of the n-Hexadecane hydrocarbon of better oilness and energy perfect combustion.These superiority impel various countries to use one after another the substitute of biofuel as fossil oil, to solve the vehicles number air pollution problems inherent of bringing of increasing sharply.
Along with developing rapidly and commercial applications of biofuel, also produce some other problem simultaneously.One of them critical problem is, utilize vegetables oil by transesterification reaction production biofuel process in, inevasiblely can produce a large amount of cheap by-product glycerins.By stoichiometric equation, the quality that we can calculate by-product glycerin easily accounts for 10% of biofuel overall productivity.Since two thousand, because European yield of biodiesel is every year with 28% speed rapid growth, be expected to reach 1,014 ten thousand tons to the annual production of European biofuel in 2012.And in the U.S., the annual production of biofuel has also reached 300,000,000 gallons.According to estimates, in ensuing several years, the output of the annual biofuel of the U.S. also will increase by 600,000,000 gallons.Federal government of Canada also requires the annual production of biofuel in 2010 to reach 500,000,000 liters, to meet the requirement of the Kyoto Protocol.In Asia, Malay biofuel annual production target is 500,000 tons.Along with the demand of biofuel is increasing, the output of raw glycerine is also increasing, also causes glycerine market value to drop fast simultaneously, and this will bring huge challenge to how reasonably processing glycerine.The scale operation of biofuel is the surplus of 80～88% raw glycerine by causing purity.Common application approach and current glycerine market cannot digest these raw glycerines.Because the purity requirement of industrial application glycerine reaches 98%, this certainly will require the glycerine of these 80～88% purity to carry out purifying, and purge process will spend great amount of cost.The report of Tyson2003 is pointed out, considers the value of glycerine, and the production cost of biofuel can be reduced to 0.38 dollar every liter by 0.63 dollar every liter, also will further drop.
Glycerine has good application prospect at automobile and biorefinery industry, can be translated into fuel oil additive.Glyceryl ether is the valuable replacing fuel oil additive knowing at present.Glycerine and iso-butylene generation etherification reaction, obtain the tertiary butyl glyceryl ether mixture that contains a tertiary butyl glyceryl ether (MTBGs), di-t-butyl glyceryl ether (DTBG), tri-tert glyceryl ether (TTBG).After glycerine etherificate, owing to having generated ehter bond, there is variation in the polarity of product.Wherein, a tertiary butyl glyceryl ether is polar material, water soluble; Di-t-butyl glyceryl ether and tri-tert glyceryl ether are apolar substances, water insoluble, can be miscible with apolar substances such as diesel oil.The oxygen level of di-t-butyl glyceryl ether and tri-tert glyceryl ether is higher, is respectively 23.5% and 18.5%, far above the oxygen level of biofuel 11%.As fuel dope, higher oxygen level is conducive to fuel composition burning, can effectively reduce the quantity discharged of particulate matter, smog and carbon monoxide.The motor-method octane number (MON) of di-t-butyl glyceryl ether, tri-tert glyceryl ether is respectively 91 and 99, and research octane number (RON) (RON) is respectively 112 and 128.Therefore, glyceryl ether can be used as good octane rating promoter.In addition, can also be used as diesel oil low temperature flow properties improver, reduced viscosity additive and the uprising additive of gasoline, as the substitute of methyl tertiary butyl ether (MTBE) and Ethyl Tertisry Butyl Ether (ETBE).
Chinese patent (application number 200810012271.3) discloses a kind of method of preparing glycerin ether from glycerol, and the method is with tosic acid, Amberlyst35, Nafion NR50, S
2o
8 -2/ ZrO
2-Fe
2o
3-SiO
2, H
3pW
12o
4/ MCM-41, H beta-molecular sieve, the vitriol oil, trifluoroacetic acid, N-(4-sulfonic group) butyl-pyridinium dihydrogen phosphate, SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2-MnO
3or 1-methyl-3-acetoxyl imidazole bisulfate is catalyzer, catalyzing glycerol reacts with methyl tertiary butyl ether, ethyl cyclohexyl tertbutyl ether, methyl-phenoxide, 1-triacontanol, methyl alcohol or nhepene and generates glyceryl ether.But there is a problem in this method, utilize methyl tertiary butyl ether, ethyl cyclohexyl tertbutyl ether, methyl-phenoxide, 1-triacontanol, methyl alcohol or nhepene and glycerine reaction to generate glyceryl ether, the transformation efficiency of glycerine is not high, and the Bronst of H beta-molecular sieve catalyst surface acid density is low, be unfavorable for the carrying out of glycerine etherification reaction.
Summary of the invention
The object of the invention is the not high deficiency of transformation efficiency of the low and glycerine of the Bronst acid density of the H beta-molecular sieve catalyst surface that overcomes prior art, and a kind of new synthetic process of tertiary butyl glyceryl ether is provided.
For reaching above object, the present invention takes following technical scheme to be achieved:
Utilize rare-earth modified molecular-sieve to prepare a technique for tertiary butyl glyceryl ether, it is characterized in that, comprise the steps:
(1) rare earths salt that is 0.1-1mol/L with deionized water compound concentration, by 1: the solid-to-liquid ratio of 10-50 is mixed β or H beta-molecular sieve with rare earths salt, heated and stirred is carried out ion-exchange, then drying and calcining, obtain rare earth modified β or H beta-molecular sieve catalyzer, wherein, rare earth comprises one or more of lanthanum, cerium, neodymium, europium, samarium, praseodymium;
(2) selecting glycerine and iso-butylene is reaction raw materials, and the mol ratio of glycerine and iso-butylene is 1: 2～6, adds 1～10% rare earth modified β or H beta-molecular sieve catalyzer of qualities of glycerin in reaction raw materials;
(3) reaction mass of step (2) preparation is joined in reactor, pass into N
2the air in still is swept in air-blowing, then uses N
2gas is pressurized to 1Mpa～2MPa, and the heating material in reactor is stirred, and reaction 1～8h obtains tertiary butyl glyceryl ether.
In above-mentioned technique, the described rare-earth salts of step (1) is rare earth nitrate, lanthanon acetate, rare earth sulfate or rare earth chloride.Described heated and stirred is to adopt microwave in 100 DEG C of following heating, and churning time is 10～60min.Described drying and calcining is vacuum-drying 2h at 120 DEG C, then at 200～300 DEG C, calcines 2～6h.The described temperature of reaction of step (3) is 50～100 DEG C, and stirring velocity is 800～1200rpm.
Tool of the present invention has the following advantages:
1, by ion-exchange, rare earth ion has strengthened the Bronst acid density on H beta-molecular sieve surface, is conducive to the carrying out of etherification reaction, has improved glycerol conversion yield.
2, by ion-exchange, rare earth ion has strengthened the thermostability of H beta-molecular sieve, and its strong-electromagnetic field effect is conducive to activate iso-butylene.
3, H beta-molecular sieve is after rare earth modified, and microvoid structure remains unchanged, and is conducive to reduce the generation of tri-tert glyceryl ether, has improved the selectivity of di-t-butyl glyceryl ether, has reduced the consumption of iso-butylene, is conducive to reduce the production cost of glyceryl ether.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
It is reaction raw materials that the present invention selects glycerine and iso-butylene, under the condition of rare earth modified β or H beta-molecular sieve catalyzer, can synthesize the tertiary butyl glyceryl ether that obtains high yield, and reaction formula is as follows:
Embodiment 1
A. prepare 250mL, the lanthanum nitrate hexahydrate of 1.0mol/L, took the beta-molecular sieve of 25g than 1: 10 by solid, joined in 500mL glass flask, and 10min is stirred in microwave heating at 100 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 6h at 200 DEG C.
B. take respectively 92g glycerine (1mol) and 9.2g lanthanum modification H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1Mpa.Then pump into the liquid iso-butylene of 540mL (6mol) by high-pressure pump, temperature is controlled at 100 DEG C, stirring velocity is set to 800rpm, reaction 1h obtains tertiary butyl glyceryl ether, the transformation efficiency of its glycerine is 81.1%, the selectivity of the di-t-butyl glyceryl ether in gained tertiary butyl glyceryl ether is 54.3%, and the selectivity of tri-tert glyceryl ether is 9.1%.
Embodiment 2
A. prepare 250mL, the cerous acetate solution of 0.8mol/L, took the beta-molecular sieve of 12.5g than 1: 20 by solid, joined in 500mL glass flask, and 30min is stirred in microwave heating at 90 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 6h at 200 DEG C.
B. take respectively the cerium modified H beta-molecular sieve of 92g glycerine (1mol) and 7.36g, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1Mpa.Then pump into the liquid iso-butylene of 360mL (4mol) by high-pressure pump, temperature is controlled at 80 DEG C, stirring velocity is set to 800rpm, reaction 2h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 83.4%, the selectivity of di-t-butyl glyceryl ether is 60.5%, and the selectivity of tri-tert glyceryl ether is 8.6%.
Embodiment 3
A. prepare 250mL, the Neodymium sulfate solution of 0.6mol/L, took the beta-molecular sieve of 8.33g than 1: 30 by solid, joined in 500mL glass flask, and 60min is stirred in microwave heating at 90 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 4h at 250 DEG C.
B. take respectively 92g glycerine (1mol) and 7.36g neodymium modification H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1.5Mpa.Then pump into the liquid iso-butylene of 270mL (3mol) by high-pressure pump, temperature is controlled at 70 DEG C, stirring velocity is set to 800rpm, reaction 2h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 91.9%, the selectivity of di-t-butyl glyceryl ether is 61.3%, and the selectivity of tri-tert glyceryl ether is 8.4%.
Embodiment 4
A. prepare 250mL, the Europium trichloride solution of 0.4mol/L, took the beta-molecular sieve of 6.25g than 1: 40 by solid, joined in 500mL glass flask, and conventional heating stirs 1h at 90 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 4h at 250 DEG C.
B. take respectively 92g glycerine (1mol) and 3.68g europium modification H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1Mpa.Then pump into the liquid iso-butylene of 270mL (3mol) by high-pressure pump, temperature is controlled at 60 DEG C, stirring velocity is set to 1000rpm, reaction 6h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 87.8%, the selectivity of di-t-butyl glyceryl ether is 62.6%, and the selectivity of tri-tert glyceryl ether is 7.2%.
Embodiment 5
A. prepare 250mL, the samarium nitrate solution of 0.2mol/L, took the beta-molecular sieve of 5g than 1: 50 by solid, joined in 500mL glass flask, and conventional heating stirs 4h at 90 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 2h at 300 DEG C.
B. take respectively 92g glycerine (1mol) and 1.84g samarium modification H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1Mpa.Then pump into the liquid iso-butylene of 270mL (3mol) by high-pressure pump, temperature is controlled at 60 DEG C, stirring velocity is set to 1000rpm, reaction 6h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 80.5%, the selectivity of di-t-butyl glyceryl ether is 53.5%, and the selectivity of tri-tert glyceryl ether is 5.8%.
Embodiment 6
A. prepare 250mL, the praseodymium nitrate solution of 0.1mol/L, took the beta-molecular sieve of 5g than 1: 50 by solid, joined in 500mL glass flask, and conventional heating stirs 8h at 100 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 2h at 300 DEG C.
B. take respectively 92g glycerine (1mol) and 0.92g praseodymium modification H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1Mpa.Then pump into the liquid iso-butylene of 180mL (2mol) by high-pressure pump, temperature is controlled at 50 DEG C, stirring velocity is set to 1200rpm, reaction 8h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 48.2%, the selectivity of di-t-butyl glyceryl ether is 39.8%, and the selectivity of tri-tert glyceryl ether is 4.2%.
Embodiment 7
A. prepare 250mL, the Neodymium sulfate of 0.6mol/L, lanthanum nitrate, acetic acid europium solution, took the beta-molecular sieve of 8.33g than 1: 30 by solid, joins in 500mL glass flask, and 60min is stirred in microwave heating at 90 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 4h at 250 DEG C.
B. take respectively 92g glycerine (1mol) and 7.36g neodymium modification H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1.5Mpa.Then pump into the liquid iso-butylene of 270mL (3mol) by high-pressure pump, temperature is controlled at 70 DEG C, stirring velocity is set to 800rpm, reaction 2h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 92.2%, the selectivity of di-t-butyl glyceryl ether is 62.8%, and the selectivity of tri-tert glyceryl ether is 8.9%.
Embodiment 8
A. prepare 250mL, the samaric nitrate of 0.6mol/L, Cerium II Chloride, praseodymium acetate solution, took the beta-molecular sieve of 8.33g than 1: 30 by solid, joins in 500mL glass flask, and 60min is stirred in microwave heating at 90 DEG C, carries out ion-exchange.After filtering, with deionized water wash, 120 DEG C of vacuum-drying 2h, calcine the beta-molecular sieve catalyzer that obtains lanthanum modification after 4h at 250 DEG C.
B. take respectively 92g glycerine (1mol) and 7.36g neodymium modification H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1.5Mpa.Then pump into the liquid iso-butylene of 270mL (3mol) by high-pressure pump, temperature is controlled at 70 DEG C, stirring velocity is set to 800rpm, reaction 2h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 92.7%, the selectivity of di-t-butyl glyceryl ether is 61.9%, and the selectivity of tri-tert glyceryl ether is 9.4%.
Comparative example
Take respectively 92g glycerine (1mol) and 0.92g H beta-molecular sieve, join in 1L stainless steel cauldron, pass into N
2purge the air in still, then use N
2be pressurized to 1Mpa.Then pump into the liquid iso-butylene of 180mL (2mol) by high-pressure pump, temperature is controlled at 50 DEG C, stirring velocity is set to 1200rpm, reaction 8h obtains tertiary butyl glyceryl ether, the transformation efficiency of glycerine is 44.2%, the selectivity of di-t-butyl glyceryl ether is 34.8%, and the selectivity of tri-tert glyceryl ether is 3.2%.
From above result, the glycerol conversion yield that proves the embodiment 1,2,3,4,5,6 of validity of the present invention is respectively: 81.1%, 83.4%, 91.9%, 87.8%, 80.5%, 48.2%, 92.2%, 92.7%, and the selectivity of di-t-butyl glyceryl ether is 54.3,60.5%, 61.3%, 62.6%, 53.5%, 39.8%, 62.8%, 61.9%; And the glycerol conversion yield of comparative example is 44.2%, the selectivity of di-t-butyl glyceryl ether is 34.8%.Be not difficult to find out that synthetic route of the present invention significantly improves the transformation efficiency of glycerine and the selectivity of di-t-butyl glyceryl ether.
Claims (2)
1. utilize rare-earth modified molecular-sieve to prepare a technique for tertiary butyl glyceryl ether, it is characterized in that, comprise the steps:
(1) rare earths salt that is 0.1-1mol/L with deionized water compound concentration, pressing the solid-to-liquid ratio of 1:10-50 mixes β or H beta-molecular sieve with rare earths salt, heated and stirred is carried out ion-exchange, then drying and calcining, obtain rare earth modified β or H beta-molecular sieve catalyzer, wherein, rare earth comprises one or more of lanthanum, cerium, neodymium, europium, samarium, praseodymium, described heated and stirred adopts microwave in 100 DEG C of following heating, churning time is 10～60min, described drying and calcining is vacuum-drying 2h at 120 DEG C, then at 200～300 DEG C, calcines 2～6h;
(2) selecting glycerine and iso-butylene is reaction raw materials, and the mol ratio of glycerine and iso-butylene is 1:2～6, adds 1～10% rare earth modified β or H beta-molecular sieve catalyzer of qualities of glycerin in reaction raw materials;
(3) reaction mass of step (2) preparation is joined in reactor, pass into N
2the air in still is swept in air-blowing, then uses N
2gas is pressurized to 1MPa～2MPa, and the heating material in reactor is stirred, and reaction 1～8h obtains tertiary butyl glyceryl ether.
2. the technique of utilizing rare-earth modified molecular-sieve to prepare tertiary butyl glyceryl ether as claimed in claim 1, is characterized in that, the described rare-earth salts of step (1) is rare earth nitrate, lanthanon acetate, rare earth sulfate or rare earth chloride.
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| CN103910612B (en) * | 2014-03-06 | 2015-08-19 | 大连大学 | A kind of method of catalyst etherifying preparing glycerin ether from glycerol |
| CN108002987B (en) * | 2016-10-28 | 2022-01-04 | 中国石油化工股份有限公司 | Method and system for preparing glycerin alkyl ether by two-step method |
| CN106831360B (en) * | 2017-01-16 | 2020-05-05 | 南京师范大学 | Process method for continuously preparing β -naphthyl methyl ether |
| CN109422627B (en) * | 2017-08-22 | 2021-09-07 | 中国石油化工股份有限公司 | Method for preparing tert-butyl glyceryl ether by glycerol etherification |
| CN109810734A (en) * | 2019-02-13 | 2019-05-28 | 郑州星创能源科技有限公司 | Methanol fuel anti-knock agent and methanol fuel containing the anti-knock agent |
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| KR20100097938A (en) * | 2009-02-27 | 2010-09-06 | 지에스칼텍스 주식회사 | Method of manufacturing glycerol di-t-butyl ether |
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| KR20100097938A (en) * | 2009-02-27 | 2010-09-06 | 지에스칼텍스 주식회사 | Method of manufacturing glycerol di-t-butyl ether |
| CN101773848A (en) * | 2010-01-14 | 2010-07-14 | 华东理工大学 | Catalyst used for synthesizing methyl tertiary butyl ether and preparation method thereof |
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| 喻顺祥等.稀土浸渍处理对β沸石结构、酸性和催化性能的影响.《石油学报》.1998,第14卷(第14期),30-34. |
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