CN104312639B - A kind of polyether class clean diesel oxygenatedchemicals and preparation method thereof - Google Patents

A kind of polyether class clean diesel oxygenatedchemicals and preparation method thereof Download PDF

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CN104312639B
CN104312639B CN201410554070.1A CN201410554070A CN104312639B CN 104312639 B CN104312639 B CN 104312639B CN 201410554070 A CN201410554070 A CN 201410554070A CN 104312639 B CN104312639 B CN 104312639B
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oxygenatedchemicals
high temperature
vapour pressure
polyether class
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赵鉴明
李茂盛
李德治
杨思祖
杨思念
赵俊
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SHANGHAI QIANMAO CHEMICAL TECHNOLOGY Co Ltd
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Abstract

The present invention relates to clean energy field, especially relate to a kind of polyether class clean diesel oxygenatedchemicals and preparation method thereof.Described oxygenatedchemicals, be prepared from by the following method, etherificate intermediate, thermally splitting diesel component, high temperature anticoking agent 1: 1: 0.00017-0.0008 are dropped into reactor in mass ratio, vacuumize, be heated with stirring to 373-438 DEG C, saturation vapour pressure 1-3Mpa, releases, gets product after heat exchanger water cooling.Beneficial effect of the present invention is: react with methyl alcohol and trioxymethylene the alkene that the intermediate and shale oil that generate polyether class or coalite tar thermally splitting generate, hybrid reaction generates PODE polymkeric substance and diesel component, both can add in diesel oil with arbitrary proportion and used as diesel oil oxygenation agent, simultaneously can also diesel oil substitute; The methyl alcohol not yet utilized and shale oil, coalite tar are used and produces polyether class clean diesel oxygenatedchemicals, achieve the maximum exploitation of resource; In addition, its preparation technology is simple, saves cost of investment.

Description

A kind of polyether class clean diesel oxygenatedchemicals and preparation method thereof
Technical field
The present invention relates to clean energy field, especially relate to a kind of polyether class clean diesel oxygenatedchemicals and preparation method thereof.
Background technology
Polyoxymethylene dimethyl ethers (polymethoxydimethylether, PODE) is the low-molecular-weight acetal polymer that is main chain with sub-methoxyl group.General formula: CH 3(OCH 2) noCH 3, be high boiling liquid.The compound of n=3-6 is that a kind of diesel oil oxygenation agent of excellent property is also referred to as polyether class clean diesel oxygenatedchemicals.Add 5% ~ 15% in diesel oil, (diesel oil is oxygen-free), oxygenation 2.35% ~ 7%, can improve efficiency of combustion.
Due to natural oil resource-constrained, oil price rises steadily, and countries in the world are all in the substitute of making great efforts development research oil, and shale oil is a kind of paraffinic based oil being rich in alkane, alkene, aromatic hydrocarbons, is an emerging energy industry.The shale oil reserves of China are only second to Russia and the United States, rank third place in the world.U.S.'s shale oil thermally splitting hydrogenation produces gasoline, diesel oil.Vigorous shale oil revolution becomes a fraud of the world today, and its major cause is that cost is more expensive than oil.
The mature production technology of methyl alcohol, cost is low, output is large; China's methanol output 2878.54 ten thousand tons in 2013, coalite tar output about 2,000 ten thousand tons, paraformaldehyde, trioxymethylene output about 8,000,000 tons, shale oil output only more than 200 ten thousand tons.China's year in 2013 consumption diesel oil is more than 1.5 hundred million tons.But the product utilizing methyl alcohol and shale oil, coalite tar to produce polyether class clean diesel oxygenatedchemicals does not still find.
Summary of the invention
For the weak point existed in the problems referred to above, the present invention utilizes methyl alcohol and shale oil, coalite tar to produce polyether class clean diesel oxygenatedchemicals.
For achieving the above object, the invention provides a kind of polyether class clean diesel oxygenatedchemicals, be prepared from by the following method, by etherificate intermediate, thermally splitting diesel component, high temperature anticoking agent 1:1:0.00017-0.0008 input reactor in mass ratio, vacuumize, be heated with stirring to 374-438 DEG C, saturation vapour pressure 1-5MPa, releases rapidly, gets product after heat exchanger water cooling, i.e. polyoxymethylene dimethyl ethers, also referred to as polyether class clean diesel oxygenatedchemicals; Through distillation, initial boiling point: the light oil about 7% ~ 8% of 60 DEG C ~ 170 DEG C, 170 DEG C ~ 360 DEG C about 90%, more than 360 DEG C 2% ~ 3%.Finished product yield: gasoline component 7%, polyether series products 90%, loss 2%.
Wherein said etherificate intermediate is prepared by the following method: methyl alcohol, trioxymethylene, MCM-56 high-silica zeolite catalyzer, high temperature anticoking agent are dropped into reactor according to mass ratio 4:1:0.0125-0.025:0.0006-0.00125, the hydroxyl of methyl alcohol is combined with alkene and open loop aromatic hydrocarbons, vacuumize, be heated with stirring to 400-450 DEG C, saturation vapour pressure 20-30MPa, be water-cooled to after normal temperature through heat exchanger rapidly and release, become etherificate intermediate, described etherificate intermediate after testing, density: 0.785kg/ liter, boiling range; Initial boiling point: 70 DEG C, 50% recovered temperature: 110 DEG C, do: 125 DEG C, through gas chromatographic analysis; Methanol content :=3%, PODE:=2 ~ 40%, PODE:=3 ~ 15%, PODE:=4 ~ 4%, PODE:=5 ~ 2%.
The intermediate about 30% of other ether, calorific value: 36800kJ/kg, color: water white.Smell: ether taste.
The preparation method of described thermally splitting diesel component is: shale oil or coalite tar, high temperature anticoking agent are dropped into reactor according to mass ratio 1:0.0006-0.00125, vacuumize, be heated with stirring to 460-470 DEG C, saturation vapour pressure 6-8MPa, release after heat exchanger water cooling rapidly, temperature is down to 60 DEG C, become thermally splitting diesel component, boiling range: initial boiling point: ~ 170 DEG C, 50%: ~ 300 DEG C, 85%: ~ 360 DEG C, more than 360 DEG C residual oil 15%.
Become diesel component through the shale oil of thermally splitting or coalite tar, 60 DEG C of temperature, with 5% hydrogen peroxide+(0.1% phospho-wolframic acid+1% methyl alcohol), mixing, stir, washing 20min, precipitation 30min, filters throw out.
Phospho-wolframic acid (phosphotungsticacid), be called for short: PTA, molecular weight: 2880.05 is the strongest heteropolyacids, miscible with water, methyl alcohol, ethanol, acetonitrile, after mixing with hydrogen peroxide in the present invention, to sulphur, phenol (alkali nitrogen) oxidation removal, be used as complex catalyst, addition: 0.1% ~ 0.2%.
Hydrogen peroxide, is commonly called as: hydrogen peroxide, chemical formula: H 2o 2molecular weight: 34.01 colourless liquids, boiling point: 150 DEG C, flash-point: 107.35 DEG C, miscible with water, methyl alcohol, ethanol, ether, acetonitrile, by concentration in the present invention: the aqueous solution of <30% and phospho-wolframic acid are misciblely oxidized, complex catalyst, addition 5%, to sulphur, phenol, (alkali nitrogen), there is strong oxidation, for desulfurization, dealkalize nitrogen.Remove oil product peculiar smell and bleaching action, resultant: oxygen+(with) water.
Survey pH value after washing, if pH value is in about 6.5 slightly acidics and qualified, as pH value is acid below 6, by the alkaline solution stirring and washing of 15% mass percentage concentration, finally uses clean water again, after precipitation, water is put into treatment tank process.Oil product is as clear as crystal, and pH value is slightly acidic, adds 0.001% ~ 0.006% p-ten.-butylcatechol (antioxidant, stablizer) immediately, detects: sulphur content≤50PPM, alkali nitrogen≤50PPM, becomes thermally splitting diesel component.
P-ten.-butylcatechol (para-tert-butylcatechol), be called for short: TBE, molecular weight: 166.22, flash-point: 151 DEG C, boiling point: 285 DEG C, is dissolved in methyl alcohol, ethanol, ether, acetone, and product has the crystalline powder of 4-TBE content > 99% and another kind of liquid product, as polymerization retarder, oxidation inhibitor, the stablizer of alkene, synthetic rubber, nylon, lubrication wet goods product, color preserving agent, addition: 0.001% ~ 0.006%.
Shale oil is a kind of artificial petroleum, and its character is close to oil.Component is similar to coalite tar.Its component is very complicated, boiling point: 170 DEG C ~ 520 DEG C, open flash point: 100 DEG C ~ 110 DEG C, density: 0.9kg/L ~ 0.96kg/L, calorific value: 41000kJ/kg.Described shale oil and coalite tar calorific value high, density is large, macromole is many; Use high temperature thermal cracking method, by the chain rupture of macromole Long carbon chain, generate an alkene and an alkane.As with C 16h 34n-Hexadecane thermally splitting, C-C bond rupture, is reacted into: C 8h 18octane and C 8h 16octene.After shale oil or coalite tar thermally splitting, there are higher alkene and alkane.
Preferred: described etherificate intermediate is prepared by the following method: methyl alcohol, trioxymethylene, MCM-56 high-silica zeolite catalyzer, high temperature anticoking agent are dropped into reactor according to mass ratio 4:1:0.0125:0.0002, vacuumize, be heated with stirring to 430 DEG C, saturation vapour pressure 25MPa, release after heat exchanger water cooling rapidly, become etherificate intermediate.
Preferred: the preparation method of described thermally splitting diesel component is: shale oil, high temperature anticoking agent are dropped into reactor according to mass ratio 1:0.0002, vacuumize, be heated with stirring to 460 DEG C, saturation vapour pressure 6MPa, release after heat exchanger water cooling rapidly, become thermally splitting diesel oil.
Preferred: described polyether class multienzyme class clean diesel oxygenatedchemicals becomes, etherificate intermediate, thermally splitting diesel component, high temperature anticoking agent are dropped into reactor according to mass ratio 1:1:0.00027, vacuumize, be heated with stirring to 430 DEG C, saturation vapour pressure 3MPa, release after heat exchanger water cooling rapidly, get product.
Preferred: wherein said methyl alcohol is ammonia from coal, molecular formula: CH 3oH, relative molecular weight: 32.04, boiling point: 64.51 DEG C, density: 0.792kg/L, burning-point: 470 DEG C, flash-point: 12 DEG C, calorific value: 19300KJ/Kg.Its methanol content is: 99.9%, and methyl alcohol is the simplest saturated monohydroxy alcohol of a kind of structure, is obtained by carbon monoxide and H-H reaction.
Preferred: wherein said trioxymethylene is the product of methyl alcohol and formaldehyde reaction, Chinese another name 1.3.5 mono-or three pentane.1.3.5 trioxane.Symmetrical three oxygen six rings, the own ring of trioxa, trioxane is needle-like crystal.Boiling point 114.5 DEG C, density 1.17kg/ liter, water-soluble, the organic solvent such as alcohol, ether.
Preferred: wherein said MCM-56 high-silica zeolite catalyzer is the new-type high silicon molecular sieve catalyst of Mobil company of U.S. research and development, be a kind of with the strongly-acid mesopore molecular sieve of the silicon and aluminum source synthesis such as micro-pore zeolite, U-4527, silicon sol, water glass.In the condensation reaction of methyl alcohol and trioxymethylene, add MCM-56 high-silica zeolite catalyzer 1% ~ 2%, do catalyzed reaction agent and use, more effective than other an acidic catalysts, especially other an acidic catalyst safety is used to environmental protection ratio.
Preferred: the SSH-18 scorch inhibitor that wherein said high temperature anticoking agent is produced by Jiangsu Taihu Chemical Co., Ltd., density: 0.9903kJ/kg, viscosity: 60.1mm 2s, open flash point: 100 DEG C, condensation point :-15 DEG C, pH value: 7.4, outward appearance: brown liquid, oil soluble: good.High temperature anticoking agent is formulated by the block polyether of molecular weight 5000 ~ 12000, tetramethylolmethane ether, sulfenic acid acid amides and aviation kerosene.Be the indispensable additive of the present invention, otherwise high-temperature scaling can blocking pipe.
High temperature anticoking agent, be added in the raw material of all heat, the homolytic reaction of free radical can be promoted, reduce cracked gas to generate, there is anti-oxidant and metal passivation effect, dirty thing is suppressed to generate, there is high temperature resistant dissemination, being dissolved by the superpolymer of generation is dispersed in liquid oil, suppress metallic surface foulant to generate, keep metallic surface to clean, addition: 0.005% ~ 0.03%, different with Heating temperature depending on oil product, addition is completely different, shale oil and coalite tar addition are 0.02%.Thermally splitting C-C bond rupture, temperature must reach 460 DEG C ~ 470 DEG C, all can fouling in reactor, tubular oven, pipeline reactor, pipeline at all raw materials of this temperature.High temperature anticoking agent prevents fouling in thermal cracking process exactly.
Beneficial effect of the present invention is: the present invention's methyl alcohol and trioxymethylene react the alkene that the intermediate and shale oil that generate polyether class or coalite tar thermally splitting generate, hybrid reaction generates the PODE polymkeric substance of 60% and the diesel component of 40%, both can add in diesel oil with arbitrary proportion and used as diesel oil oxygenation agent, simultaneously can also diesel oil substitute; The methyl alcohol not yet utilized and shale oil, coalite tar are used and produces polyether class clean diesel oxygenatedchemicals, achieve the maximum exploitation of resource, energy-conserving and environment-protective; In addition, its preparation technology is simple, only has 3 steps, saves cost of investment.
Accompanying drawing explanation
Fig. 1 is a kind of polyether class clean diesel oxygenatedchemicals preparation flow figure of the present invention.
Embodiment
Embodiment 1:
As shown in the figure, preparation of the present invention is undertaken by following steps,
Step 101: the preparation of etherificate intermediate
After above four kinds of raw materials mixing, put into 2000ml reactor, vacuumize, heat while stirring, record oil temperature, saturation vapour pressure, heat-up time.
Oil temperature 30 DEG C, saturation vapour pressure 0MPa, heat-up time 0.Oil temperature 72 DEG C, saturation vapour pressure 2MPa, heat-up time 10min.Oil temperature 118 DEG C, saturation vapour pressure 3MPa, heat-up time 12min.Oil temperature 209 DEG C, saturation vapour pressure 4MPa, heat-up time 14min.Oil temperature 222 DEG C, saturation vapour pressure 5MPa, heat-up time 15min.Oil temperature 238 DEG C, saturation vapour pressure 7MPa, heat-up time 16min.Oil temperature 248 DEG C, saturation vapour pressure 8MPa, heat-up time 18min.Oil temperature 258 DEG C, saturation vapour pressure 9MPa, heat-up time 19min.Oil temperature 430 DEG C, saturation vapour pressure 25MPa, heat-up time 48min.
Above etherificate intermediate is water-cooled to normal temperature through heat exchanger, does and distill: initial boiling point: 70 DEG C, 50%:95 DEG C, final boiling point: 125 DEG C, density: (20 DEG C) 0.79kg/L.Calorific value: 36800KJ/Kg, colourity: No. 1.5.Methanol etherification intermediate accounts for about 65% ~ 70%.
Step 102: the preparation of thermally splitting diesel component
(1) shale oil 1000g
(2) high temperature anticoking agent 0.2g
Two kinds of material stirrings are even, put into 2000ml reactor, vacuumize.Heat while stirring, oil temperature is record from normal temperature, start oil temperature 349 DEG C, saturation vapour pressure 0.1MPa, heat-up time 11min.Oil temperature 394 DEG C, saturation vapour pressure 1MPa, heat-up time 27min.Oil temperature 439 DEG C, saturation vapour pressure 2MPa, heat-up time 34min.Oil temperature 444 DEG C, saturation vapour pressure 3MPa, heat-up time 37min.Oil temperature 453 DEG C, saturation vapour pressure 4MPa, heat-up time 40min.Oil temperature 459 DEG C, saturation vapour pressure 5MPa, heat-up time 42min.Oil temperature 460 DEG C, saturation vapour pressure 6MPa, heat-up time, 44min started thermo-negative reaction, and oil temperature starts to drop to 458 DEG C, saturation vapour pressure 6.5MPa, heat-up time 45min.Oil temperature drops to 456 DEG C, saturation vapour pressure 7Mpa, heat-up time 47min.Oil temperature drops to 453 DEG C, saturation vapour pressure 8MPa, heat-up time 48min.
Can analyze out from above second step, shale oil thermally splitting be endothermic cracking from oil temperature 460 DEG C of saturation vapour pressure 6MPa, and oil temperature is down to 453 DEG C, saturation vapour pressure 8MPa, heat-up time 48min.Reactor oil temperature is dropped to 453 DEG C of saturation vapour pressure 8MPa from 460 DEG C, during 48min heat-up time, stops heating immediately.Rapidly shale oil in reactor is water-cooled to normal temperature from delivery valve through heat exchanger.Boiling range :≤170 DEG C of products: nothing.170 DEG C ~ 350 DEG C yield, more than 85%, 350 DEG C residual oil 15%.To thermally splitting 170 DEG C of-360 DEG C of products: 850g of normal temperature be cooled to, add hydrogen peroxide: 42.5g, phospho-wolframic acid: 0.85g, methyl alcohol: 8.5g mix and blend, cleaning 20 minutes.After precipitation, water is released, then use the liquid caustic soda of 42.5g concentration 20%, stirring and washing 20 minutes, after precipitation, buck is put into treatment tank.Throw out is filtered.Again with 5% clear water wash one time, precipitation after water is put into treatment tank.Check by biodiesel technology requirement.170 DEG C ~ 350 DEG C components, cold filter clogging temperature :-3 DEG C, density: 0.83, colourity: No. 3, viscosity: 6mm 2/ s, cetane value: 58, close flash point: 90 DEG C, boiling range: initial boiling point 170 DEG C, 50% vaporization temperature: 300 DEG C, 85%, vaporization temperature: 350 DEG C, more than 360 DEG C residual oil 15%, sulphur content: <50PPM, alkali nitrogen: <50PPM.
Step 103: prepared by finished product
(1) etherificate intermediate 750g
(2) thermally splitting diesel component 750g
(3) high temperature anticoking agent 0.2g
Drop into 2000ml reactor, vacuumize, stir and heat.Record as follows:
Above mixture is heated to 438 DEG C, saturation vapour pressure 3MPa.Stop heating, be water-cooled to normal temperature rapidly through interchanger, through distillation: <170 DEG C about 7% ~ 8%, 170 DEG C ~ 350 DEG C about 90%, >=360 DEG C about 2% ~ 3%.
Send Shanghai Chemical Research Inst to check finished product, be reported as follows:
(1) colourity: No. 1.5 (2) copper corrosions: (50 DEG C/3h) level 1a
(3) moisture content %: vestige (4) mechanical impurity: nothing
(5) kinematic viscosity: (mm 2/ s) 4.3 (6) sulphur content % (massfraction): 0.0049
(7) cold filter clogging temperature: DEG C-12 (8) flash-points: (remaining silent) DEG C: 75
(9) cetane value: 52 (10) density: (20 DEG C) (kg/m 3) 810
(11) boiling range: 50% vaporization temperature 263 DEG C, 90% vaporization temperature 333 DEG C, 95% vaporization temperature 338 DEG C.
(12) calorific value: (kJ/kg) 46490 (13) methanol content: do not detect
Above test item, totally 13, index is all better than-No. 10 state IV biodiesel technology indexs.
Embodiment 2:
Substantially the same manner as Example 1, unlike:
Step 101: the preparation of etherificate intermediate
Final oil temperature 400 DEG C, saturated vapor pressure 20MPa;
Step 102: the preparation of thermally splitting diesel component
(1) shale oil 1000g
(2) high temperature anticoking agent 0.125g
Oil temperature is heated to 470 DEG C, saturated vapor pressure 8MPa, carries out endothermic cracking afterwards, when temperature drops to 453 DEG C, during saturated vapor pressure 8MPa, rapidly shale oil in reactor is water-cooled to normal temperature from delivery valve through heat exchanger.
Step 103: prepared by finished product
(1) etherificate intermediate 750g
(2) thermally splitting diesel component 750g
(3) high temperature anticoking agent 0.125g
Outlet temperature 373 DEG C, saturated vapor pressure 1MPa;
Product performance prepared by the present embodiment are better than-No. 10 state IV biodiesel technology indexs, if the methyl alcohol production capacity that the whole nation 50% not yet goes into operation all uses produce polyether class clean diesel oxygenatedchemicals with shale oil, coalite tar, can diesel oil substitute 5,000 ten thousand tons/year, be equivalent to 30% of national diesel oil total amount.
Embodiment 3:
Substantially the same manner as Example 1, unlike:
Step 101: the preparation of etherificate intermediate
Final oil temperature 450 DEG C, saturated vapor pressure 30MPa;
Step 102: the preparation of thermally splitting diesel component
(1) shale oil 1000g
(2) high temperature anticoking agent 0.6g
Step 103: prepared by finished product
(1) etherificate intermediate 750g
(2) thermally splitting diesel component 750g
(3) high temperature anticoking agent 0.6g
Owing to only relating to 3 step reactions, reaction conditions comparatively easily realizes, and saves cost of investment, uses, cost-saving 600 yuan/ton according to calculating according to diesel oil, if carry out use according to diesel oil oxygenation agent, saves about 1000 yuan/ton of cost.
Only as described above, be only preferred embodiment of the present invention and oneself, professional who are familiar with this art such as, after understanding technique means of the present invention, natural energy, according to actual needs, is changed under the teachings of the present invention.Therefore all equal changes of doing according to the present patent application the scope of the claims and modification, all should still remain within the scope of the patent.

Claims (8)

1. a polyether class clean diesel oxygenatedchemicals, it is characterized in that being prepared from by the following method, etherificate intermediate, thermally splitting diesel component, high temperature anticoking agent 1: 1: 0.00017-0.0008 are dropped into reactor in mass ratio, vacuumize, be heated with stirring to 373-438 DEG C, saturation vapour pressure 1-3MPa, releases, gets product after heat exchanger water cooling;
Wherein said etherificate intermediate is prepared by the following method: methyl alcohol, trioxymethylene, MCM-56 high-silica zeolite catalyzer, high temperature anticoking agent are dropped into reactor according to mass ratio 4: 1: 0.0125-0.025: 0.000125-0.0006, vacuumize, be heated with stirring to 400-450 DEG C, saturation vapour pressure 20-30MPa, release after heat exchanger water cooling, become etherificate intermediate;
The preparation method of described thermally splitting diesel component is: shale oil or coalite tar, high temperature anticoking agent are dropped into reactor according to mass ratio 1: 0.0006-0.00125, vacuumize, be heated with stirring to 460-470 DEG C, saturation vapour pressure 6-8MPa, release after heat exchanger water cooling, become thermally splitting diesel component;
Described high temperature anticoking agent is formulated by the block polyether of molecular weight 5000 ~ 12000, tetramethylolmethane ether, sulfenic acid acid amides and aviation kerosene, density: 0.9903kJ/kg, viscosity: 60.1mm 2s, open flash point: 100 DEG C, condensation point :-15 DEG C, pH value: 7.4.
2. polyether class clean diesel oxygenatedchemicals according to claim 1, it is characterized in that: described etherificate intermediate is prepared by the following method: methyl alcohol, trioxymethylene, MCM-56 high-silica zeolite catalyzer, high temperature anticoking agent are dropped into reactor according to mass ratio 4: 1: 0.0125: 0.0002, vacuumize, be heated with stirring to 430 DEG C, saturation vapour pressure 25MPa, be water-cooled to after normal temperature through heat exchanger and release, become etherificate intermediate.
3. polyether class clean diesel oxygenatedchemicals according to claim 1, it is characterized in that: described polyether class clean diesel oxygenatedchemicals, etherificate intermediate, thermally splitting diesel component, high temperature anticoking agent are dropped into reactor according to mass ratio 1: 1: 0.00027, vacuumize, be heated with stirring to 430 DEG C, saturation vapour pressure 3MPa, is water-cooled to after normal temperature through heat exchanger and releases, get product.
4. polyether class clean diesel oxygenatedchemicals according to claim 1, is characterized in that: wherein said methyl alcohol is ammonia from coal.
5. polyether class clean diesel oxygenatedchemicals according to claim 1, is characterized in that: wherein said trioxymethylene is the product of methyl alcohol and formaldehyde reaction.
6. polyether class clean diesel oxygenatedchemicals according to claim 1, is characterized in that: wherein said MCM-56 high-silica zeolite catalyzer is the new-type high silicon molecular sieve catalyst of Mobil company of U.S. research and development.
7. polyether class clean diesel oxygenatedchemicals according to claim 1, is characterized in that: the SSH-18 scorch inhibitor that wherein said high temperature anticoking agent is produced by Jiangsu Taihu Chemical Co., Ltd..
8. a preparation method for the polyether class clean diesel oxygenatedchemicals as above described in any one claim, is characterized in that making in accordance with the following steps:
(1) preparation of etherificate intermediate
Methyl alcohol, trioxymethylene, MCM-56 high-silica zeolite catalyzer, high temperature anticoking agent are dropped into reactor according to mass ratio 4: 1: 0.0125-0.025: 0.000125-0.0006, vacuumize, be heated with stirring to 400-450 DEG C, saturation vapour pressure 20-30MPa, release after heat exchanger water cooling, become etherificate intermediate;
(2) preparation of thermally splitting diesel component
Shale oil or coalite tar, high temperature anticoking agent are dropped into reactor according to mass ratio 1: 0.0006-0.00125, vacuumizes, be heated with stirring to 460-470 DEG C, saturation vapour pressure 6-8MPa, release after heat exchanger water cooling, become thermally splitting diesel component;
(3) preparation of finished product
Etherificate intermediate, thermally splitting diesel component, high temperature anticoking agent are dropped into reactor according to mass ratio 1: 1: 0.00017-0.0008, vacuumizes, be heated with stirring to 374-438 DEG C, saturation vapour pressure 1-3MPa, release after heat exchanger water cooling, get product.
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