CN1160745A - 柴油机用粘稠烃包水乳液燃油以及制法 - Google Patents

柴油机用粘稠烃包水乳液燃油以及制法 Download PDF

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CN1160745A
CN1160745A CN97100711A CN97100711A CN1160745A CN 1160745 A CN1160745 A CN 1160745A CN 97100711 A CN97100711 A CN 97100711A CN 97100711 A CN97100711 A CN 97100711A CN 1160745 A CN1160745 A CN 1160745A
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赫西列奥·里瓦斯
古斯塔沃·A·努涅斯
图利奥·科曼纳尔斯
曼努埃尔·奇里诺斯
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/022—Adding fuel and water emulsion, water or steam
    • F02M25/0228—Adding fuel and water emulsion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/4105—Methods of emulsifying
    • 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
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B47/00—Methods of operating engines involving adding non-fuel substances or anti-knock agents to combustion air, fuel, or fuel-air mixtures of engines
    • F02B47/02—Methods of operating engines involving adding non-fuel substances or anti-knock agents to combustion air, fuel, or fuel-air mixtures of engines the substances being water or steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/505—Mixing fuel and water or other fluids to obtain liquid fuel emulsions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

一种柴油机用燃油以及制备体烃包水形式乳液的方法，其中平均水滴直径小于等于4微米，最大水滴直径小于等于10微米。

Description

柴油机用粘稠烃包水乳液燃油以及制法
本发明涉及一种利用粘稠烃作柴油机用燃料，以及一种燃料产物的方法。
已知本领域中用天然存在的沥青，或者渣油中制成水包烃乳液，目的是为生产和/或运输这些粘稠的烃。美国专利3,380,531；3,467,195；3,519,006；3,943,954；4,099,537；4,108,193；4,239,052以及4,570,656记载了这种典型的方法。除此之外，现有技术还披露从天然沥青和/或渣油制成的水包烃乳液(hydrocarbon in water emulsions)可以用做燃料。请参见美国专利4,144,015；4,378,230；4,618,348和英国专利文献974,042。
如上所述的水包烃乳液，它可以在某些发电厂内用做燃料，诞生不适合于在柴油机，特别是低速柴油机内燃烧。自然，人们一直渴望能使用粘稠的天然沥青和/或渣油作为柴油机的燃料。
本发明之主要目的在于提供一种使用粘稠烃(viscous hydrocarbon)作为柴油机的燃料的方法。
本发明这特殊目的在于提供一种前述的方法，其中所述的粘稠烃为为天然状态的沥青或者渣油。
本发明之另一目的在于提供一种烃包水乳液(a water in hydrocarbonemulsion)形式的柴油机用燃料。
本发明的目的以及优点将在以下得以阐明。
本发明涉及一种利用一种粘稠烃作为柴油机燃料油，以及燃料油产品的方法。
根据本发明的方法，用粘稠烃制成水包烃乳液，目的是使得有利于该粘稠烃的生产和运输到燃烧部位。水包烃乳液可用公知的方法制备，如US专利4,801,304；4,795,476；4,834,775；4,923,483，4,824,439；4,994,090；4,776,977；4,781,819；4,806,231；和4,915,819中所披露的方法。另外已知的制备水包烃乳液的方法在US专利4,934,398；4,618,348；4,666,457；4,684,372；和4,793,826也有描述。
按照本发明的方法，采用烃水比例为60∶40至90∶10，优选在65∶35至75∶25能够制成水包烃乳液。使用非-离子表面活性剂制备水包烃乳液。非-离子表面活性剂在乳液中的含量为大于或等于2000ppm。要求非-离子表面活性剂含有的环氧乙烷的数量大于或者等于10，优选为10-100之间。可用于本发明方法的粘稠烃是具有API比重小于或等于16API度，以及122华氏度黏度大于或等于100cPs。
上述的水包烃乳液可以采用升高温度，在高温下混合来对水包烃乳液加热来将其转化，从而将水包烃乳液转化成烃包水乳液。按照本发明，关键的是得到的烃包水乳液产物具有的平均水滴直径小于或等于4微米(um)，最大落滴直径小于或等于10微米(um)。为了获得用与柴油机的燃料油产品，就必须要控制烃包水乳液的水滴直径。以下因素能够控制水滴的直径：
1为了转化而加热水包烃乳液的加热温度，
2非-离子表面活性剂的浓度；
3非-离子表面活性剂的环氧乙烷(EO)含量；
4在转化方法中使用的混合能量；以及
5在原始水包烃乳液内的烃水比例。
特别是，发生转化时的温度和混合能量，随着表面活性剂的浓度和EO含量的增加和烃含量的减少而增加。
水滴大小的控制以及得到的烃包水乳液的关键在于(1)水的存在允许柴油机内更充分的燃烧，(2)水滴小能帮助雾化，(3)低温下能充分燃烧燃油，导致少形成NOX产物以及少形成碳黑。
以下将详细描述本发明的进一步的优点和特征。
本发明涉及一种利用一种粘稠烃，以烃包水乳液的形式作为柴油机燃油，以及燃油产品的方法。
适用于本发明方法的粘稠烃包括天然沥青和渣油，其特征为它的API比重为小于或等于16API度，其122华氏度的黏度大于或等于100cPs。为了运输的目的，要处理这些本发明之粘稠烃，处理方法为制成水包烃乳液。按照本发明的方法，要形成水包烃乳液就要采用非离子表面活性剂作为乳化剂。水包烃乳液的特征为其烃水比例为约60∶40到90∶10，优选为65∶35到75∶25。要求非-离子表面活性剂含有的环氧乙烷的数量大于或者等于10，优选为10-100之间。非-离子表面活性剂在乳液中的含量为大于或等于2000ppm。用现有技术公知的方法可以制成水包烃乳液。例如这些方法披露与US专利4,776,977和4,934,398以及其他的上述讨论过的材料中。
为了得到一种粘稠烃燃料油，必须要把上述的水包烃乳液转化烃包水乳液。按照本发明之方法，柴油机合适的燃料油包括一种烃包水乳液，其中它的乳液中水滴的大小要在临界值之内。以发现为了在低温下获得更充分的燃烧，少形成氧化氮和碳黑，柴油机适用的烃包水乳液燃料油的平均水滴直径必须小于等于4微米，最大水滴直径小于或等于10微米。这种燃料油乳液产物的水烃比例约为40∶60到10∶90，优选为约35∶75到25∶75，非离子表面活性剂的含量等于2000ppm，而EO含量优选介于10-100，这样该产物可以在低温下有效地被雾化，而且充分燃烧。当水滴直径超过上述的临界值时，油料的雾化不完全，大大降低燃烧效率，而燃烧要求高温，因此，形成大量的碳黑和NOX污染物。
柴油机使用的烃包水乳液燃料产物可以通过对水包烃乳液进行控制的转化方法，从用于运输粘稠烃而形成的水包烃乳液中得到。根据本发明，水包烃乳液在高温下进行转化，即大于或等于90摄氏度，临界混合能为大于等于6×106J/立方米，从而将该乳液转化成具有所要求的包括平均和最大值的水滴直径的烃包水乳液。
通过在转化过程中控制温度和混合能来控制乳液的转化，其中所述的温度是非离子表面活性剂的浓度和EO含量的函数，而混合能是水包烃乳液中烃含量的函数。温度要求大于等于90℃，混合能大于或等于6.00×106J/立方米。从以下的实施例将进一步明了，该转化方法为一个温度，混合能，以及非离子表面活性剂(EO含量)，乳液内表面活性剂的量，以及粘稠烃的性质和烃含量的函数。
本发明的优点将在如下实施例中进一步阐明。
实施例1
取四份水包烃乳液样品，其用于转化时的烃水比例为70∶30，其中粘稠烃的API比重为8.5度，86华氏度时的黏度为700cPs。使用非离子表面活性剂制成这四份样品，其表面活性剂的浓度为3000ppmEO含量分别为13，17，33和38。将每一种样品度加热到80，90，100℃，8.5×106J/立方米用混合能混合。监测转化成乳液所需的时间，得到的水滴平均和最大直径。其结果见表1。
                      表1
                    温度(℃)
表面活性剂EO     80        90       100
    13173338     22秒     10秒      5秒280秒    200秒     80秒800秒    600秒    250秒1200秒    800秒    350秒
平均水滴直径
    最大平均    20μm    10μm     6μm10μm    15μm     2μm
从表内可见，转化时间随着EO含量增加而延长，随温度降级而缩短。包括最大和平均(max and mean)的平均水滴直径(average drop diameter)随温度的降低而变小。
实施例2
按实施例1所述的方法制备另外的乳液，其中要把烃的含量降低到75∶25到80∶20。将该乳液进行转化，转化温度为90℃，混合能8.5×106J/立方米。结果见表2。
                 表2
               烃含量(％)
表面活性剂EO     70       75        80
    13173338     10秒     10秒      4秒200秒    100秒     20秒600秒    100秒     30秒800秒    120秒     35秒
平均水滴直径
    最大平均     8μm     8μm     6μm4μm     4μm     2μm
从表2中可以看出，随着烃含量增加，转化时间随平均水滴直径的变小而缩短。
实施例3
按照实施例2的方法制备乳液，不同的是表面活性剂的浓度降低到2000ppm。其结果见表3。
                   表3
                 温度(℃)
表面活性剂EO     80       90        100
    13173338     20秒     10秒      5秒200秒    100秒     60秒500秒    300秒    100秒700秒    400秒    200秒
平均水滴直径
    最大平均    25μm     8μm     5μm10μm     4μm     2μm
从表中可见，随着表面活性剂的浓度降低转化时间的缩短，平均水滴直径为温度的函数。
实施例4
按照实施例1的方法制备乳液，使用的表面活性剂的环氧乙烷(EO)含量为17。在变化的温度和混合能条件下，转化该乳液。其结果见表4和表5。
                                  表4
混合能(106J/m3)     3.6    8.5    13.1   15.5
    温度℃9095100 800    200    180    120400    150     60     40320    100     50     10
             表5
温度为90℃处，混合能     平均水滴直径(106J/m3)            最大  平均
    3.6                    15    88.5                    10    513.1                    6    315.5                    5    2
表4，表5中可以看出，随着平均水滴直径变小，混合能增加。
从以上的表述可以见，本发明的方法使得以在烃乳液内以水的形式形成燃料油，这种水形式可将利用粘稠烃作为低速柴油机的燃油。
本发明也可以以其他方式不超出其本质特征或发明构思来实施。上述的实施例仅为说明起见，而非限定之意。任何来自本范围和其等同物的变换都将包括本发明之保护范围之内。

Claims (4)

1.使用粘稠烃作为柴油机的燃油的方法，包括：
(A)提供一种水包烃乳液，其烃水比例为60∶40到90∶10，非离子表面活性剂的含量为大于或等于2000ppm，所述的烃的特征为API比重小于或等于16度API，122华氏度黏度大于或等于100cPs，所述的表面活性剂含有的环氧乙烷(EO)含量为大于或等于10；
(B)将所述的水包烃乳液加温和混能，使得将所述的水包烃乳液转化成烃包水乳液，其特征为平均水滴直径小于或等于4微米(um)，最大水滴直径小于或等于10微米(um)，其中，升高的温度随着表面活性剂中环氧乙烷含量的增加而增高，混合能随着烃含量的减少而增加；
(C)雾化所述的烃包水乳液；以及
(D)在柴油机内燃烧所述的烃包水乳液。
2.如权利要求1所述的方法，其中所述的升高的温度为大于或等于90℃，所述的混合能为大于或等于6.0×106J/立方米。
3.如权利要求1所述的方法，其中所述的环氧乙烷(EO)含量介于10到100之间。
4.一种柴油机用燃油，包括一种其烃水比例为40∶60到10∶90之间的烃包水乳液，和含量大于或等于2000ppm的非离子表面活性剂，所述的烃的特征为其API比重小于等于10度API，122华氏度的黏度大于或等于100cPs，所述的非离子表面活性剂内含有环氧乙烷的量为大于或等于10，所述的烃包水乳液的特征为平均水滴直径小于等于4微米(um)，最大水滴直径小于等于10微米(um)。
CN97100711A 1996-02-09 1997-02-05 柴油机用粘稠烃包水乳液燃油以及制法 Expired - Fee Related CN1128857C (zh)

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CN1102952C (zh) * 1997-04-11 2003-03-12 英特卫普有限公司 蒸汽转化方法和催化剂

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US5725609A (en) 1998-03-10
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