CN1045789C - 柴油组合物 - Google Patents
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- 239000002283 diesel fuel Substances 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 167
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000446 fuel Substances 0.000 claims description 44
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 230000014509 gene expression Effects 0.000 claims description 5
- 239000002551 biofuel Substances 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
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- 239000007789 gas Substances 0.000 description 4
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
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- 238000002485 combustion reaction Methods 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- UEMGPPRIYDXNGE-UHFFFAOYSA-N C(C)(=O)O.C(CCCCC)O[N+](=O)[O-] Chemical compound C(C)(=O)O.C(CCCCC)O[N+](=O)[O-] UEMGPPRIYDXNGE-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSNWZBCBUUSSQD-UHFFFAOYSA-N amyl nitrate Chemical compound CCCCCO[N+]([O-])=O HSNWZBCBUUSSQD-UHFFFAOYSA-N 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
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- 239000003500 flue dust Substances 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 239000000779 smoke Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种柴油组合物,含有约70-95%(wt)的二甲醚、最多可达约20%(wt)的甲醇以及约0.1-20%(wt)的水。
Description
发明背景
发明技术领域
本发明主要涉及一种柴油组合物,尤其是涉及一种含有二甲醚、甲醇和水的柴油组合物。
现有技术描述
作为通过精炼石油制备出的通用烃类柴油的代用燃料品,自本世纪二十年代起,人们一直在考虑通过转化甲烷或煤而获得其它液体燃料,甲醇一直被当作内燃机使用的这样一种代用燃料,它通常是由一氧化碳和氢制取,以往大量地或者由天然气或者由煤制得。一氧化碳基本上也是由任何一种含碳物质制得的,该含碳物质包括农产品、林业产品及许多废弃物。生产甲醇用的原材料供量大及来源广满足了作为内燃机燃料使用增长速度快的要求。但是,甲醇热值即BTU值很低,所以,当采用甲醇作为燃料时,内燃机的工作性能大大下降。
与甲醇相反,二甲醚BTU值较高并且无毒,另外,二甲醚是一种清洁燃料,其燃料气体中基本上无固体颗粒存在。已经有许多方法被披露了,都是用于由从各种原材料如天然气、燃或者基本上所有种含碳物质获取的合成气体生产结合有甲醇和水的二甲醚。这类公开的具体材料有Bell等人的美国专利4,341,069、Van Dijk等人的美国专利5,177,114和已公开的欧洲专利申请0324475及0409086A1,特别是上述最后的两篇欧洲专利申请0324475及0409086A1公开了在这样一种方法中如何控制工艺条件,以便生产具有较高二甲醚与甲醇摩尔比的二甲醚混合物。
在用于生产二甲醚的许多方法中,二甲醚是以一种产品混合物的形式而被生产出来的,该产品混合物也含有甲醇和/或水,而且,在这种产品混合物中,要想从二甲醚中除去甲醚和水就需要有附加的加工步骤。因此,非常理想的是能够采用二甲醚、甲醇和水的混合物即(换言之)粗或未精炼二甲醚直接作为柴油燃料,以便省掉与提纯粗二甲醚相关的上述附加的加工步骤,所以就可以采用直接从合成气体生产这类混合物的加工条件。采用这种方法,可以省掉或者至少可以使对附加的加工步骤如提纯步骤的需求减少到最低程度,而且还能够生产出高效及经济的代用柴油。
也有许多其它有关柴油类的公开材料,这类柴油包括一种二甲醚与甲醇的混合物、一种二甲醚与甲醇及水的混合物、或者一种二甲醚与十六烷值改进剂的混合物,例如,德国专利654,470(1937)介绍了二甲醚与甲醇的混合物,含有5-45%的甲醇(以及55-95%的二甲醚),作为内燃机的燃料使用,该燃料具有相对高的二甲醚热值可以被利用,同时,避免由于二甲醚在火花点着发动机时出现的震动现象而造成的过度的质量下降。
还有,Norton在美国专利4,422,412介绍了一种柴油组合物,它含有二甲醚、甲醇和水的混合物,其二甲醚含量“最多可达约50%,例如约为5~30%”。通过在出口与内燃机汽缸相连的反应器中使甲醇与二甲醚及水进行催化转化而制备这种混合物。
另外,Norton等人在美国专利4,603,662中介绍了一种柴油组合物,含有至少一种醚、至少一种醇及可选择的附加成分如水或十六烷值改进剂的混合物,该混合物中有“按体积计燃料中醚类含量为5~80%,较好的是5-20%”。该项专利披露,含有二甲醚与甲醇混合物的燃料是一种特别通用的燃料,并且具体说明这种混合物燃料含有:(a)在实施例1和3中按体积计95%的甲醇和5%的二甲醚;以及(b)在实施例5.1中有78%的甲醇和20%的二甲醚。该项专利也包括以下具体说明的醇类与醚类混合物,其所含的醚类至少为50%:(a)在实施例5.9中为80%的(二)异戊醚和20%的甲醇;(b)在实施例6.2中为60%的二正丙醚及40%的甲醇;以及在实施例6.5中为60%的二正丁醚和40%的甲醇。
Levine在美国专利4,892,561中介绍了第一种柴油组合物,含有95-99.9%(wt)的二甲醚和0.1~5%(wt)的十六烷值改进剂;该项专利还介绍了第二种柴油组合物,含有至少50%(wt)的上述第一种柴油,余量为通用的烃类柴油。
但是,到目前为止,一直无人公开下述的由二甲醚、甲醇和水混合的组合物,它含有使所生产的柴油同时具有利于环境保护及良好点火性能所必需的二甲醚、甲醇及水的平衡浓度,不需要进行高成本投入的提纯步骤便可进行经济规模的批量生产,而且,该柴油在贮存及使用时都能以稳定的单一液相存在。
发明目的
本发明的主要目的是提供一种克服上述缺陷且具有上述优点的改进型代用柴油组合物。
更具体地讲,本发明的目的是提供一种具有高BTU值的改进型代用柴油组合物。
本发明的另一个目的是提供一种为清洁燃料材料的改进型代用柴油组合物,其总排放物较低,其燃烧气体基本上无固体颗粒存在。
本发明的再一个目的是提供一种具有极好点火性能的改进型代用柴油组合物。
本发明的又一个目的是提供一种不必用高成本提纯步骤便可以进行经济有效地生产的改进型代用柴油组合物。
本发明还有一个目的就是提供一种在使用时及在贮存期间都能以稳定的单一液相而存在的改进型代用柴油组合物。
在阅读以下的详细说明及所附的权利要求书时,使会对本发明的其它一些目的及其优点有清楚的理解。
发明概要
本发明的这些目的可以用下述的改进型柴油组合物获得,该组合物由约70-95%(wt)的二甲醚、约0.1-20%(wt)的水以及最多可达约20%(wt)的甲醇组成,其中在含有给定的水浓度(wt%)(水浓度)的柴油组合物中所允许的最小甲醇浓度(wt%)(最小甲醇浓度)按下列关系式确定:
0≤最小甲醇浓度≥0.5(水浓度)-2.6而且,在含有给定的水浓度(wt%)(水浓度)的柴油组合物中所允许的最大甲醇浓度(wt%)(最大甲醇浓度)由以下关系式确定:
最大甲醇浓度≤20-0.6(水浓度)。
发明详细说明
本发明的组合物是一种柴油组合物,含有二甲醚、甲醇及水的混合物,在本发明的代用柴油组合物中所含二甲醚的量为约70(wt),较好的是约85%(wt)至95%(wt),较好的是93%(wt)。如果本发明的代用柴油组合物含有低于约70%(wt)的二甲醚,柴油点火性能差及其分成两种液相问题便会防碍该柴油组合物作为柴油的有效使用。
水在本发明的代用柴油组合物中的含量为约0.1%(wt),较好的是约1%(wt),约2%(wt)则更好,至20%(wt),较好的是至10%(wt)。本发明的组合物只有二甲醚与水形成混合物时,如果水含量超过约5.2%(wt),就会使组合物分离,形成两种液相,除非还有甲醇存在。
在下述的限量以内,在二甲醚与水的混合物中有一定量的甲醇存在就能使该混合物稳定,防止其分离成两种液相。作为这种稳定作用所必须的甲醇含量随着在水与二甲醚形成混合物中水浓度的增加而增加。但是,如果在含有特定水浓度的混合物中甲醇含量过大,则混合物的点火性能就会受到不利影向。所以,对于二甲醚与给定水浓度的混合物,甲醇在这种混合物中的浓度必须至少为一确定的最小量,以便防止相分离,而且又必须小于一确定的最大量,以免出现点火性能下降。
甲醇在混合物中规定最大及最小浓度取决于在该混合物中特定的水浓度,并且随着该特定的水浓度的大小而变化。在柴油中甲醇的最小浓度(wt%)(最小甲醇浓度)取决于在含有给定水浓度的该柴油中的水浓度(wt%)(水浓度),并且由下列近似关系式确定:
0≤最小甲醇浓度≥0.5(水浓度)-2.6。
在含有给定水浓度的柴油中甲醇的最大浓度(wt%)(最大甲醇浓度)由以下近似关系式确定:
最大甲醇浓度≤20-0.6(水浓度)。
以上两个近似关系式都是根据使用大量的含二甲醚、甲醇及水的不同混合物,实际测定点火性能及相分离状况而进行经验性地确定的。
如上述两个关系式所示,除非柴油组合物中含有至少5.2%(wt)的水,否则,不必使本发明的代用柴油组合物中有甲醇存在。另外,在任何情况下,在本发明代用柴油组合物中能够含有的最大甲醇浓度为20%(wt),还有,当本发明代用柴油组合物含有20%(wt)的水时,该柴油组合物必须也含有至少7.4%(wt)的甲醇,以便防止出现相分离,而且,甲醇含量必须不超过8%(wt),否则,就会导致点火性能差。为了所有的实用目的,该有效的甲醇浓度范围就是要这样窄,在本发明代用柴油组合物中能够含有的水浓度上限为20%(wt)。
在另一个优选的实施方案中,为了改进本发明代用柴油组合物的点火性能,可以向柴油组合物中以十六烷值改进剂最加入任何一种适宜的通用十六烷值改进剂。适用的十六烷值改进剂的具体例子包括无机过氧化物如过氧化氢、有机过氧化物如乙基叔丁基过氧化物及二叔丁基过氧化物、硝酸烷基酯如己基硝酸乙酸、硝酸戊酯以及硝基甲烷。更具体地讲,在柴油组合物中使用十六烷值改进剂,其浓度在较好的约为0.01%(wt),最好约为0.05%(wt)至较好约为3%(wt),最好约为1%的范围之内。
在另一个优选的实施方案中,本发明代用柴油组合物还可以含有最高可达50%(wt)的通用烃类柴油或由植物类制取的生物柴油。
从以下特别实施例可以更加清楚地理解本发明。用具有90度V-8、位移444立方英寸、内孔径4.11英寸及冲程4.18英寸的Navistar T444E型柴油机对含有94%(wt)的二甲醚、3%水(wt)及3%(wt)甲醇的柴油组合物进行试验,该柴油机是一种汽轮增压器,装有气-气中间冷却器、电控直接喷射柴油系统以及配有废气循环系统。对于这项试验,由于为了获得与通用烃类柴油相同的动力输出而必须喷射更多的DME,使用了尺寸稍微过大的喷射器。另外,由于试验用的含二甲醚组合物的较高挥发特性,采用了改进型的供料泵,以便防止在喷射器中形成柴油气蚀。采用模拟美国EPA瞬时试验循环制的8型稳态试验循环制进行发动机试验,对下列废气排放物进行测量:烃类、一氧化碳、氧化氮、烟尘及颗粒物。
试验结果表明,当氧化氮排放量为5gm/bhp-hr时,含二甲醚组合物的消耗量基本与通用柴油的相同,而当氧化氮排放量低于3 64gm/bhp-hr时,含二甲醚组合物的消耗量便大大地小于通用柴油的消耗量。氧化氮排放物的量只有约1.7gm/bhp-hr,与只有纯二甲醚的氧化氮排放物的量相比大有改进。排放物的烟尘含量仅为约0.03gm/bhp-hr,烃类排放物的量为约0.3gm/bhp-hr,只略高于纯二甲醚排放物的对应量。在这项试验中测量出的(1)氧化氮与烃类排放物的总量为约2.1gm/bhp-hr与(2)排放物中颗粒物的量为约0.034gm/bhp-hr已经都落在按加利福尼亚州ULEV要求遵循的自1998年以后开始生效的各自上限2.5gm/bhp-hr和0.05gm/bhp-hr之内。
根据以上说明,很明显,本发明的目的已经得到实现,已经列出的只有几个实施方案,对本领域中普通技术人员来讲,从以上的说明中会很明显地理解,其它一些实施方案及多种变更都被认为是等同的,并属于本发明的精神及范围之内。
以上已经说明了本发明的内容,以下内容是本发明的权利要求。
Claims (9)
1.一种柴油组合物,由70-95%(wt)的二甲醚、1-20%(wt)的水以及1-20%(wt)的甲醇组成,其中在含有给定的水浓度(wt%)(水浓度)的柴油组合物中所允许的最小甲醇浓度(wt%)(最小甲醇浓度)按下列关系式确定:
0≤最小甲醇浓度≥0.5(水浓度)-2.6而且,在含有给定的水浓度(wt%)的柴油组合物中所允许的最大甲醇浓度(wt%)(最大甲醇浓度)由以下关系式确定:
最大甲醇浓度≤20-0.6(水浓度)。
2.根据权利要求1所述的柴油组合物,含有2~10%(wt)的甲醇。
3.根据权利要求1所述的柴油组合物,含有2~20%(wt)的水。
4.根据权利要求1所述的柴油组合物,含有2~10%(wt)的水。
5.根据权利要求1所述的柴油组合物,含有2~10%(wt)的甲醇,以及2~10%(wt)的水。
6.根据上述权利要求中任何一项所述的柴油组合物,还含有0.01~3%(wt)的至少一种十六烷值改进剂。
7.根据权利要求6所述的柴油组合物,含有0.05~1%(wt)的至少一种十六烷值改进剂。
8.一种柴油组合物,含有权利要求1的柴油组合物与最多可达50%(wt)的通用烃类柴油的混合物。
9.一种柴油组合物,含有权利要求1的柴油组合物与最多可达50%(wt)的取自于植物类之生物柴油的混合物。
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US28993394A | 1994-08-12 | 1994-08-12 | |
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US9255051B2 (en) | 2013-03-15 | 2016-02-09 | Gas Technologies Llc | Efficiency, flexibility, and product value of a direct alkanes to oxygenates process |
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US6270541B1 (en) | 2001-08-07 |
NO970601L (no) | 1997-04-09 |
FI970575A (fi) | 1997-04-08 |
EP0775185A1 (en) | 1997-05-28 |
EP0775185B1 (en) | 1998-09-02 |
MX9701096A (es) | 1998-03-31 |
CN1156475A (zh) | 1997-08-06 |
CA2197201C (en) | 2004-07-06 |
WO1996005274A1 (en) | 1996-02-22 |
ES2120221T3 (es) | 1998-10-16 |
CA2197201A1 (en) | 1996-02-22 |
NO970601D0 (no) | 1997-02-10 |
JP3001263B2 (ja) | 2000-01-24 |
DE69504523T2 (de) | 1999-01-28 |
FI970575A0 (fi) | 1997-02-11 |
ATE170545T1 (de) | 1998-09-15 |
HK1003438A1 (en) | 1998-10-30 |
ZA956333B (en) | 1996-03-11 |
NZ290675A (en) | 1997-12-19 |
JPH10504054A (ja) | 1998-04-14 |
DE69504523D1 (de) | 1998-10-08 |
EG21063A (en) | 2000-10-31 |
AU3148195A (en) | 1996-03-07 |
DK0775185T3 (da) | 1999-02-08 |
RU2141995C1 (ru) | 1999-11-27 |
NO317939B1 (no) | 2005-01-10 |
BR9508565A (pt) | 1997-08-12 |
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