CN102173984A - Method for preparing low-polymerization-degree polyformaldehyde dialkyl ether from petroleum fractions and application - Google Patents
Method for preparing low-polymerization-degree polyformaldehyde dialkyl ether from petroleum fractions and application Download PDFInfo
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- CN102173984A CN102173984A CN201110067378XA CN201110067378A CN102173984A CN 102173984 A CN102173984 A CN 102173984A CN 201110067378X A CN201110067378X A CN 201110067378XA CN 201110067378 A CN201110067378 A CN 201110067378A CN 102173984 A CN102173984 A CN 102173984A
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- dialkyl ether
- low
- polymerization degree
- petroleum
- polyoxymethylene
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Links
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 62
- 150000001983 dialkylethers Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003208 petroleum Substances 0.000 title claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 58
- 239000002283 diesel fuel Substances 0.000 claims abstract description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 10
- -1 polyoxymethylene Polymers 0.000 claims description 66
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 22
- 239000000446 fuel Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005120 petroleum cracking Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 239000003921 oil Substances 0.000 description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- 229960004279 formaldehyde Drugs 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000000605 extraction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000002341 toxic gas Substances 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the technical fields of energy chemical industry and clean diesel components and in particular relates to a method for preparing low-polymerization-degree polyformaldehyde dialkyl ether from main raw materials such as a petroleum C4 component, an alkadiene-removed petroleum C5 component, a catalytic cracking light petroleum 30-90-DEC C fraction low-carbon monoolefine and the like. The structural general formula of the low-polymerization-degree polyformaldehyde dialkyl ether is CnH2n+1O(CH2O)mCnH2n+1, wherein m is an integer from 1 to 5; and n is an integer from 2 to 5. The low-polymerization-degree polyformaldehyde dialkyl ether prepared by the method has a higher CN value, can be applied to diesel fuel widely and effectively without high polymerization degree and has a relatively simple preparation process. The byproducts petroleum C4 and C5 in the petroleum cracking ethylene process and the catalytic cracking petroleum 30-90-DEC C light fraction serve as the raw materials, so production cost is greatly saved by using low-carbon olefin in the raw materials, a good technical route is provided for comprehensive utilization of a large number of byproducts in the petroleum cracking process, and remarkable economic significance is achieved.
Description
Technical field
The invention belongs to derived energy chemical, clean diesel component technical field, the method and the application thereof that be specifically related to a kind ofly to utilize oil C4 component, remove oil C5 component behind the diolefine, main raw material such as 30-90 ℃ of cut low-carbon (LC) of catalytic cracking petroleum naphtha monoolefine prepare the low polymerization degree polyoxymethylene dialkyl ether.
Background technology
In recent years, along with the continuous increase of consumption of petroleum amount and the enhancing of people's Environmental awareness, to being that the emission request of pollutents such as the oil consumption of oil engine of the energy and smoke intensity is harsh day by day with the oil, a plurality of countries in the world have formulated strict environmental regulation in succession.Improve fuel qualities, reduce noxious gas emission, a kind of method easier, economic and effectively easily row is to add improving agent in fuel oil.
Cetane value (Cetane Number is hereinafter to be referred as the CN value) is an important indicator that is used for weighing the diesel oil capability of antidetonance.In diesel motor, air at first is compressed, and then diesel oil is sprayed into the combustion chamber, and diesel oil touches warm air and is vaporized at this moment, takes fire when temperature reaches spontaneous ignition temperature.Usually fuel injection beginning is called " delay period " during this period of time to spontaneous firing.The delay period of diesel oil is long, then makes the fuel accumulation that sprays in the cylinder get off, in case spontaneous combustion, the fuel that sprays into is burning simultaneously just, and the result produces " pinking " phenomenon.The delay period of high CN diesel oil is shorter than low CN diesel oil.The CN value that improves diesel oil can reduce that exhaust pollutant discharges, reduces white cigarette, cold start-up is faster.China regulation diesel oil CN can not be lower than 45, and EMA suggestion is preferably used CN greater than 50 fuel for satisfying the designed diesel motor of modern waste gas emission standard, but should not be surpassed 60.
Because the output limited (about 30%) of China's high hexadecane value straight-run diesel oil component, and the shared ratio very big (about 70%) of low-cetane catalytic cracking diesel oil component do not surpass 45 requirement so the commercially available diesel oil CN that is in harmonious proportion generally reaches.Therefore, improving diesel oil CN value is the problem that presses for solution.
(general formula is CH to polyoxymethylene dimethyl ethers
3O (CH
2O)
mCH
3) be a kind of novel cleaning oil dope, be to improve diesel combustion performance, raising CN value, reduce carbonic acid gas and NOx discharging, reduction oil consumption and reduce a kind of effective additive of discharging fume.Because of its vapour pressure, boiling point and the solubleness in oil product, the suitable polyoxymethylene dimethyl ethers (DMM that is generally 3≤m≤8 that does the oil product interpolation
3-8).
Current, production preparation at polyoxymethylene dimethyl ethers has caused extensive studies, as U.S. Pat 5746785, US 6392102, US 2008/0207954 A1 and Chinese patent CN101182367A, the method for preparing polyoxymethylene dimethyl ethers is all disclosed.But therefrom also as can be seen, dimer with m=2 in the mix products that this reaction obtains is a primary product, and the content of the polymkeric substance of the 3≤m that is suitable for adding≤8 is not high, and because the dimer that forms as primary product has lower boiling point, so reduced its flash-point too, so the mixture that its reaction obtains still remains to be discussed as the effect that additive is added into diesel oil fuel; On the other hand, because its methyl molecular weight as end group is lower, corresponding its vapour pressure and the boiling point of influencing, the polymerization degree of the feasible polyoxymethylene dimethyl ethers that adds must remain on the scope of 3≤m≤8, and high more its working condition of component and the production process of the known polymerization degree is complicated more, and this has also influenced the application of polyoxymethylene dimethyl ethers as diesel-dope.
The CN value of diesel oil fuel can increase by mixed linear ether.The Chinese patent CN101213274A of BASF AG discloses a kind of biodiesel fuel mixture that comprises polyoxymethylene dialkyl ether, has wherein added the formula RO (CH of 0.1-20% weight
2O)
nThe polyoxymethylene dialkyl ether of R, wherein R is the alkyl with 1-10 carbon atom, and n=2-10, and preferred n=3,4,5 polyoxymethylene dialkyl ether and composition thereof.Because the molecular weight as the R of end group is big slightly, so n=3,4,5 the CN value than the polyoxymethylene dialkyl ether of low polymerization degree have also reached more than 50.And because the building-up process step of the product of low polymerization degree is comparatively simple, say from production technique, make polyoxymethylene dialkyl ether have more advantage with respect to polyoxymethylene dimethyl ethers as diesel-dope.
The Chinese patent CN101198576A of BASF AG discloses a kind of method that is prepared polyoxymethylene dialkyl ether by trioxane and dialkyl ether.In this method trioxane and the dialkyl ether that is selected from dme, methyl ethyl ether and the diethyl ether are added in the reactor, and in the presence of an acidic catalyst, react, obtain being suitable for polyoxymethylene dialkyl ether as diesel fuel additive.Yet, this reaction requires the water yield that reactant and/or catalyzer introduce reaction mixture less than based on 1% of reaction mixture, this mainly is because in the presence of water or alcohol, the chemical reaction that generation can be caused a large amount of polyoxymethylene two pure and mild hemiacetals, and will form reactive azeotrope, technology more complicated in carrying out fractionation by distillation.This has also caused this reaction process harsh relatively for the requirement of reaction conditions, and is relatively strict for the requirement of reaction raw materials; On the other hand, all belong to non-common material, need prepare especially or choose, make corresponding cost increase as the trioxane and the dialkyl ether of reaction raw materials; In addition, the end group that this patent is only inquired into the polyoxymethylene dialkyl ether of preparation is the situation of methyl and ethyl, and the polymerization degree of corresponding described polyoxymethylene dialkyl ether is 2-10, and this product also still exists the existing problem of aforementioned polyoxymethylene dimethyl ether.
Summary of the invention
For this reason, technical problem to be solved by this invention is to overcome in the prior art to have relatively high expectations as the polymerization degree of the polyoxymethylene dimethyl ether of diesel-dope and causes the lower problem of effective content, and then a kind of method for preparing the low polymerization degree polyoxymethylene dialkyl ether is provided.
Further, the invention provides a kind of utilization cheaply petroleum cracking by product oil C4 component, remove oil C5 component behind the diolefine, perhaps catalytic cracking petroleum naphtha 30-90 ℃ cut prepares the method for low polymerization degree polyoxymethylene dialkyl ether as starting raw material.
Further, the present invention also provides above-mentioned low polymerization degree polyoxymethylene dialkyl ether in the application aspect diesel-dope.
For solving the problems of the technologies described above, petroleum fractions of the present invention prepares the method for low polymerization degree polyoxymethylene dialkyl ether, it is characterized in that, comprises the steps:
(1) reaction raw materials and an acidic catalyst are dropped in the reactor, feed the air in the shielding gas replacement reaction kettle, the original pressure of control reactor is 0.1-0.8MPa, and control reaction temperature 50-200 ℃ reaction is component balanced to each, is preferably reaction 10-12 hour; Described reaction raw materials comprises low-carbon alkene class material, polyoxymethylene class material and initiator, wherein:
Described low-carbon alkene class material is that general formula is C
nH
2nLow-carbon alkene in a kind of or wherein several mixture, the integer of n=2-5 wherein;
The mixture of one or more in described polyoxymethylene class substance formaldehyde or trioxymethylene, the low polymerization degree Paraformaldehyde 96;
The molar ratio of described low-carbon alkene class material and polyoxymethylene class material is 2-4:1-4, and described catalyst consumption is the 0.1-5.0% of total reaction raw material gross weight;
(2) after reaction finished, the pH value of transferring mixture was to neutrality or weakly alkaline, through separating and collect 150-340 ℃ of cut down, and made with extra care that to obtain general structure be C
nH
2n+1O (CH
2O)
mC
nH
2n+1The low polymerization degree polyoxymethylene dialkyl ether, wherein m is a numerical value identical or inequality with n, m is the integer of 1-5, n is the integer of 2-5.
Described initiator is water and/or low-carbon alcohol, described low-carbon alcohol particular methanol.The molar ratio of described initiator and described polyoxymethylene class material is 1:1-4.
Described low-carbon alkene class material is the cut under 30-90 ℃ of the oil C4 component in the petroleum fractions, the oil C5 component that removes diolefine or the catalytic cracking petroleum naphtha, and the cut under 30-70 ℃ of the preferred catalytic cracking petroleum naphtha.
The molar ratio of described low-carbon alkene class material and polyoxymethylene class material is 2-3:3-4.
Described catalyzer is storng-acid cation exchange resin or protonic acid.
Described protonic acid is a kind of or wherein several mixture in tosic acid, trifluoromethanesulfonic acid, formic acid, the phenylformic acid.
Described shielding gas is nitrogen and/or rare gas element.
The temperature of reaction of described step (1) is 70-120 ℃.
The reaction times of described step (1) is 10-12 hour.
Described reactor is the intermittent type high-pressure reactor.
A kind of diesel oil fuel is characterized in that comprising following component:
The low polymerization degree polyoxymethylene dialkyl ether that above-mentioned method prepares, 1-20wt%
Diesel oil 80-99wt%.
According to the low polymerization degree polyoxymethylene dialkyl ether that above-mentioned preparation method prepares, the CN value of described low polymerization degree polyoxymethylene dialkyl ether is greater than 55, and its boiling point is 156-340 ℃, and density is 0.88-0.97g/mL(20 ℃), flash-point is 45-75 ℃.
Oil C
5Be the C of by-product in the petroleum hydrocarbon preparing ethylene by steam cracking process
5Hydrocarbon-fraction, it forms more complicated, be rich in diolefin and monoolefine, mainly contain isoprene (2-methyl-divinyl), cyclopentadiene (being extracted with the dipolymer dicyclopentadiene usually), m-pentadiene (cis and trans 1,3-pentadiene), isopentene (2-methyl 2-butylene) also has a small amount of 1-amylene.Wherein diolefin content is 40%-55%, and monoolefine content is 15-25%.Cracking C
5Overall yield, form and to depend primarily on cracking stock character, general hydrocarbon gas (C
2-C
4Alkane) cracking gained C
5Productive rate is the 2-6% of ethylene yield; And with liquid hydrocarbon (as petroleum naphtha and solar oil) when being cracking stock, C
5Productive rate can reach the 14-20% of ethylene yield.Along with the development of petrochemical industry, be that the throughput that raw material is produced ethene constantly increases cracking C with the liquid hydrocarbon
5Resource is abundant day by day, how to utilize cracking C
5Become an importance rationally utilizing petroleum resources and reduce production cost of ethylene, increase the benefit, and caused ethylene industry and related scientific research personnel's generally attention.
In developed country, oil C
5The research of comprehensive utilization goes before far away, progressively sets up from the 70's to the eighties and perfect industrial production system.And China C
5Fraction separation and utilization still are in the infancy, up to the present, and most C
5Cut is all burnt as fuel.So, development and utilization C
5Resource has tangible economic implications.
Technique scheme of the present invention has the following advantages compared to existing technology, 1, the low polymerization degree dialkyl ether for preparing of the present invention has higher CN value, need not the very high polymerization degree simultaneously can extensively effectively be applied in the diesel oil fuel, and preparation process is simple relatively; 2, the present invention selects low-carbon (LC) monoolefine, methyl alcohol and formaldehyde (or low polymerization degree Paraformaldehyde 96) reaction for use, only can finish whole process by once feeding intake; 3, select for use by product cut oil C4, C5 in the petroleum cracking ethylene process as raw material, utilize low-carbon alkene wherein, not only saved production cost greatly, while also provides technological line preferably for the comprehensive utilization of a large amount of by products in the petroleum cracking process, has tangible economic implications; 4, select for use catalytically cracked gasoline 30-90 ℃ lighting end (preferred 30-70 ℃ of lighting end) to prepare the low polymerization degree polyoxymethylene dialkyl ether, improve the yield ratio of diesel oil, reduce the olefin(e) centent of catalytically cracked gasoline simultaneously gasoline.
Description of drawings
For the easier quilt of content of the present invention is clearly understood, below according to a particular embodiment of the invention and in conjunction with the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is a preparation method's of the present invention process flow sheet.
Reference numeral is expressed as among the figure: 1-feedstream, 2-feedstream, 3 high-pressure reactors, 4-one-level product, 5-strainer, 6-secondary products, the 7-extraction tower, three grades of products of 8-, 9-normal pressure knockout tower, 10-low boiler cut, 11-level Four product, 12-decompression separation tower, the high polymeric component of 13-, 14-target product.
Embodiment
The preparation method's of low polymerization degree polyoxymethylene dialkyl ether of the present invention chemical equation is:
C
nH
2n+H
2O→C
nH
2n+1OH （1）
C
nH
2n+1OH+mCH
2O→C
nH
2n+1O(CH
2O)
mC
nH
2n+1+H
2O （2）
Therefore, this reaction must could take place under aqueous condition, when selected reactant is anhydrous formaldehyde, anhydrous trioxymethylene or anhydrous low polymerization degree Paraformaldehyde 96, need to add a spot of methyl alcohol as initiator, in order to generate moisture with anhydrous formaldehyde or anhydrous low polymerization degree polyformaldehyde reaction, and trigger reaction and carry out, the reaction equation of this moment is:
2mCH
3OH+(CH
2O)
m→mCH
3OCH
2OCH
3+mH
2O （1）
C
nH
2n+H
2O→C
nH
2n+1OH （2）
C
nH
2n+1OH+mCH
2O→C
nH
2n+1O(CH
2O)
mC
nH
2n+1+H
2O （3）
The feedstream 1 and the feedstream 2 that comprise low-carbon alkene class material and polyoxymethylene class material respectively are conveyed into high-pressure reactor 3; drop into an acidic catalyst in the lump; feed nitrogen and/or rare gas element as the air in the shielding gas replacement reaction kettle; the original pressure position 0.1-0.8MPa of control reactor keeps 50-200 ℃ of constant temperature to react 10-12 hour down to each component reaction balance.When finishing, reaction generates the one-level product 4 that comprises the poly-(alkoxymethyl)-2 acetal of low polymerization degree.The one-level product 4 of gained from strainer 5 by and solid impurity filtered, thereby obtain not contain substantially the secondary products 6 of solid impurity, then secondary products 6 is delivered into extraction tower 7, and carries out extracting and separating after its pH is adjusted to neutrality or alkalescence.Three grades of products 8 that obtain after the extraction enter normal pressure knockout tower 9 to be separated, and its mid-boiling point (B.P) enters high-pressure reactor 3 continuation reaction again less than 150 ℃ low boiler cut 10 backflows; The level Four product 11 that other light component are formed then continues to enter decompression separation tower 12 further to be separated, separating back m〉5 high polymeric component 13 refluxes and enters high-pressure reactor 3 and participates in again reacting, the component 14 of level eventually of m=2-5 then is satisfactory target product, promptly required low polymerization degree polyoxymethylene dialkyl ether.
Embodiment 1
Utilize petroleum fractions to prepare low polymerization degree polyoxymethylene dialkyl ether C
nH
2n+1O (CH
2O)
mC
nH
2n+1Method be:
The 2:4 ratio adds oil C successively in molar ratio in the intermittent type autoclave
5, formaldehyde content 37% industrial formol, contained water can be used as initiator and participates in reaction in the industrial formol, the tosic acid that selection accounts for reactant gross weight 2% drops in the reactor as catalyzer in the lump, charge into the air in the nitrogen replacement reactor, the original pressure 0.2Mpa of control in the reactor keeps 70-90 ℃ of isothermal reaction 10 hours component balanced to each under the 100rpm rotating speed stirs.Through above-mentioned each extraction and separating technology step, separate and the final cut of collecting 150-340 ℃ after reaction finishes, with products therefrom refining after promptly.Detect as can be known through chromatography-mass spectroscopy analysis (GC-MS), each polymerization degree products distribution is: m=1,8.32%; M=2,34.5%; M=3,21.4%; M=4,7.1%; M=5,0.9%; M＞5, trace; ∑ PODAE
2-5=63.9%.59,20 ℃ of density 0.917g/cm of the cetane value of this mixing liquid
3
Add about 10% low polymerization degree polyoxymethylene dialkyl ether in diesel oil, the cetane value of gained diesel oil fuel is 47, and flash-point is 56, not only can reach the ultra-low-sulphur diesel index, can also significantly reduce NO
xDeng noxious gas emission, blowdown reduces more than 30%.
Embodiment 2:
Utilize petroleum fractions to prepare low polymerization degree polyoxymethylene dialkyl ether C
nH
2n+1O (CH
2O)
mC
nH
2n+1Method be:
The 4:1:4 ratio adds oil C successively in molar ratio in the intermittent type autoclave
4, methyl alcohol, anhydrous low polymerization degree Paraformaldehyde 96 and anhydrous formaldehyde mixture, wherein methyl alcohol is as initiator, triggering reaction carries out, the storng-acid cation exchange resin that selection accounts for reactant gross weight 5% drops in the reactor as catalyzer in the lump, charge into the air in the inert gas replacement reactor, original pressure 0.3Mpa in the control reactor keeps 90-120 ℃ of isothermal reaction 10 hours under the 100rpm rotating speed stirs.Through above-mentioned each extraction and separating technology step, separate and the final cut of collecting 150-340 ℃ after reaction finishes, with products therefrom refining after promptly.Through the chromatography-mass spectroscopy analyzing and testing as can be known, each polymerization degree products distribution is: m=1,2.7%; M=2,39.6%; M=3,19.5%; M=4,11.1%; M=5,0.75%; M＞5, trace; ∑ PODAE
2-5=70.95%.56,20 ℃ of density 0.932g/cm of the cetane value of this mixing liquid
3
Add about 5% low polymerization degree polyoxymethylene dialkyl ether in diesel oil, the cetane value of gained diesel oil fuel is 45, and flash-point is 60, not only can reach the ultra-low-sulphur diesel index, can also significantly reduce NO
xDeng noxious gas emission, blowdown reduces more than 20%.
Embodiment 3:
Utilize petroleum fractions to prepare low polymerization degree polyoxymethylene dialkyl ether C
nH
2n+1O (CH
2O)
mC
nH
2n+1Method be:
The 3:1:2 ratio adds 30-70 ℃ of cut of catalytic cracking petroleum naphtha, methyl alcohol and anhydrous trioxymethylene successively in molar ratio in the intermittent type autoclave, methyl alcohol triggers reaction as initiator to carry out, selection accounts for the trifluoromethanesulfonic acid of reactant gross weight 0.1% and the mixture of tosic acid drops in the reactor as catalyzer in the lump, charge into the air in the nitrogen replacement reactor, original pressure 0.6Mpa in the control reactor keeps 50-70 ℃ of isothermal reaction 10 hours under the 100rpm rotating speed stirs.Through above-mentioned each extraction and separating technology step, separate and the final cut of collecting 150-340 ℃ after reaction finishes, with products therefrom refining after promptly.Through the chromatography-mass spectroscopy analyzing and testing as can be known, each polymerization degree products distribution is: m=1,8.42%; M=2,43.6%; M=3,21.2%; M=4,10.6%; M=5,0.78%; M＞5, trace; ∑ PODAE
2-5=76.18%.56,20 ℃ of density 0.941g/cm of the cetane value of this mixing liquid
3
Add about 20% low polymerization degree polyoxymethylene dialkyl ether in diesel oil, the cetane value of gained diesel oil fuel is 49, and flash-point is 55, not only can reach the ultra-low-sulphur diesel index, can also significantly reduce NO
xDeng noxious gas emission, blowdown reduces more than 40%.
Embodiment 4:
Utilize petroleum fractions to prepare low polymerization degree polyoxymethylene dialkyl ether C
nH
2n+1O (CH
2O)
mC
nH
2n+1Method be:
In the intermittent type autoclave in molar ratio the 2:3 ratio to add the mixture of ethene, butylene and formaldehyde content successively be 37% industrial formol, the moisture that is contained in the industrial formol can be used as initiator triggering reaction to carry out, selection accounts for the phenylformic acid of reactant gross weight 3% and the mixture of formic acid drops in the reactor as catalyzer in the lump, charge into the air in the nitrogen replacement reactor, original pressure 0.8Mpa in the control reactor keeps 120-150 ℃ of isothermal reaction 10 hours under the 100rpm rotating speed stirs.Through above-mentioned each extraction and separating technology step, separate and the final cut of collecting 150-340 ℃ after reaction finishes, with products therefrom refining after promptly.Detect as can be known through the GC-MS method, each polymerization degree products distribution is: m=1,4.7%; M=2,30.9%; M=3,18.6%; M=4,6.7%; M=5,0.56%; M＞5, trace; ∑ PODAE
2-5=56.76%.61,20 ℃ of density 0.996g/cm of the cetane value of this mixing liquid
3
Add about 15% low polymerization degree polyoxymethylene dialkyl ether in diesel oil, the cetane value of gained diesel oil fuel is 49, and flash-point is 60, not only can reach the ultra-low-sulphur diesel index, can also significantly reduce NO
xDeng noxious gas emission, blowdown reduces more than 35%.
Embodiment 5:
Utilize petroleum fractions to prepare low polymerization degree polyoxymethylene dialkyl ether C
nH
2n+1O (CH
2O)
mC
nH
2n+1Method be:
The 4:1:1 ratio adds the mixture of propylene, methanol solution and anhydrous trioxymethylene and anhydrous formaldehyde successively in molar ratio in the intermittent type autoclave, methanol solution can be used as initiator triggering reaction to carry out, the formic acid that selection accounts for reactant gross weight 4% drops in the reactor as catalyzer in the lump, charge into the air in rare gas element and the nitrogen replacement reactor, original pressure 0.1Mpa in the control reactor keeps 150-170 ℃ of isothermal reaction 10 hours under the 100rpm rotating speed stirs.Through above-mentioned each extraction and separating technology step, separate and the final cut of collecting 150-340 ℃ after reaction finishes, with products therefrom refining after promptly.Detect as can be known through the GC-MS method, each polymerization degree products distribution is: m=1,3.7%; M=2,32.3%; M=3,11.3%; M=4,5.1%; M=5,0.66%; M＞5, trace; ∑ PODAE
2-5=49.36%.57,20 ℃ of density 0.97g/cm of the cetane value of this mixing liquid
3
Add about 10% low polymerization degree polyoxymethylene dialkyl ether in diesel oil, the cetane value of gained diesel oil fuel is 46, and flash-point is 61, not only can reach the ultra-low-sulphur diesel index, can also significantly reduce NO
xDeng noxious gas emission, blowdown reduces more than 30%.
Embodiment 6
Utilize petroleum fractions to prepare low polymerization degree polyoxymethylene dialkyl ether C
nH
2n+1O (CH
2O)
mC
nH
2n+1Method be:
The 2:1:1 ratio adds 30-90 ℃ of cut of catalytic cracking petroleum naphtha, methyl alcohol and anhydrous trioxymethylene successively in molar ratio in the intermittent type autoclave, methyl alcohol can be used as initiator triggering reaction to carry out, the storng-acid cation exchange resin that selection accounts for reactant gross weight 1% drops in the reactor as catalyzer in the lump, charge into the air in the nitrogen replacement reactor, original pressure 0.4Mpa in the control reactor keeps 170-200 ℃ of isothermal reaction 10 hours under the 100rpm rotating speed stirs.Through above-mentioned each extraction and separating technology step, separate and the final cut of collecting 150-340 ℃ after reaction finishes, with products therefrom refining after promptly.Detect as can be known through the GC-MS method, each polymerization degree products distribution is: m=1,3.7%; M=2,32.3%; M=3,11.3%; M=4,5.1%; M=5,0.66%; M＞5, trace; ∑ PODAE
2-5=49.36%.57,20 ℃ of density 0.97g/cm of the cetane value of this mixing liquid
3
Add about 10% low polymerization degree polyoxymethylene dialkyl ether in diesel oil, the cetane value of gained diesel oil fuel is 46, and flash-point is 59, not only can reach the ultra-low-sulphur diesel index, can also significantly reduce NO
xDeng noxious gas emission, blowdown reduces more than 25%.
Obviously, the foregoing description only is for example clearly is described, and is not the qualification to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of the invention.
Claims (10)
1. petroleum fractions prepares the method for low polymerization degree polyoxymethylene dialkyl ether, it is characterized in that, comprises the steps:
(1) reaction raw materials and an acidic catalyst are dropped in the reactor, feed the air in the shielding gas replacement reaction kettle, the original pressure of control reactor is 0.1-0.8MPa, and control reaction temperature 50-200 ℃ reaction is component balanced to each; Described reaction raw materials comprises low-carbon alkene class material, polyoxymethylene class material and initiator, wherein:
Described low-carbon alkene class material is that general formula is C
nH
2nLow-carbon alkene in a kind of or wherein several mixture, the integer of n=2-5 wherein;
Described polyoxymethylene class material is one or more the mixture in formaldehyde or trioxymethylene, the low polymerization degree Paraformaldehyde 96;
The molar ratio of described low-carbon alkene class material and polyoxymethylene class material is 2-4:1-4, and described catalyst consumption is the 0.1-5.0% of reaction raw materials gross weight;
(2) after reaction finished, the pH value of transferring mixture was to neutrality or weakly alkaline, through separating and collect 150-340 ℃ of cut down, and made with extra care that to obtain general structure be C
nH
2n+1O (CH
2O)
mC
nH
2n+1The low polymerization degree polyoxymethylene dialkyl ether, wherein m is a numerical value identical or inequality with n, m is the integer of 1-5, n is the integer of 2-5.
2. petroleum fractions according to claim 1 prepares the method for low polymerization degree polyoxymethylene dialkyl ether, it is characterized in that: described initiator is water and/or methyl alcohol, and the molar ratio of described initiator and described polyoxymethylene class material is 1:1-4.
3. petroleum fractions according to claim 1 and 2 prepares the method for low polymerization degree polyoxymethylene dialkyl ether, it is characterized in that: described low-carbon alkene class material is oil C4 component, remove the cut under 30-90 ℃ of the oil C5 component of diolefine or the catalytic cracking petroleum naphtha.
4. prepare the method for low polymerization degree polyoxymethylene dialkyl ether according to each described petroleum fractions of claim 1-3, it is characterized in that: the molar ratio of described low-carbon alkene class material and polyoxymethylene class material is 2-3:3-4.
5. prepare the method for low polymerization degree polyoxymethylene dialkyl ether according to each described petroleum fractions of claim 1-4, it is characterized in that: described catalyzer is storng-acid cation exchange resin or protonic acid.
6. petroleum fractions according to claim 5 prepares the method for low polymerization degree polyoxymethylene dialkyl ether, it is characterized in that: described protonic acid is a kind of or wherein several mixture in tosic acid, trifluoromethanesulfonic acid, formic acid, the phenylformic acid.
7. prepare the method for low polymerization degree polyoxymethylene dialkyl ether according to claim 1 or 2 or 3 described petroleum fractionss, it is characterized in that: described shielding gas is nitrogen and/or rare gas element.
8. prepare the method for low polymerization degree polyoxymethylene dialkyl ether according to each described petroleum fractions of claim 1-7, it is characterized in that: the temperature of reaction of described step (1) is 70-120 ℃.
9. prepare the method for low polymerization degree polyoxymethylene dialkyl ether according to each described petroleum fractions of claim 1-7, it is characterized in that: the reaction times of described step (1) is 10-12 hour.
10. diesel oil fuel is characterized in that comprising following component:
The low polymerization degree polyoxymethylene dialkyl ether that each described method of claim 1-9 prepares, 1-20wt%
Diesel oil 80-99wt%.
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| CN106520180A (en) * | 2017-01-06 | 2017-03-22 | 中国石油大学(华东) | Method for reducing olefin content of catalytically cracked gasoline |
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