CN106811227B - 一种利用能源草沼渣制备生物油的方法 - Google Patents
一种利用能源草沼渣制备生物油的方法 Download PDFInfo
- Publication number
- CN106811227B CN106811227B CN201710041910.8A CN201710041910A CN106811227B CN 106811227 B CN106811227 B CN 106811227B CN 201710041910 A CN201710041910 A CN 201710041910A CN 106811227 B CN106811227 B CN 106811227B
- Authority
- CN
- China
- Prior art keywords
- grass
- biogas residue
- energy
- energy grass
- thermal cracking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 244000025254 Cannabis sativa Species 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000012075 bio-oil Substances 0.000 title claims abstract description 15
- 238000004227 thermal cracking Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000855 fermentation Methods 0.000 claims abstract description 27
- 230000004151 fermentation Effects 0.000 claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009833 condensation Methods 0.000 claims abstract description 11
- 230000005494 condensation Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000001722 flash pyrolysis Methods 0.000 claims description 9
- 244000130556 Pennisetum purpureum Species 0.000 claims description 7
- 244000062720 Pennisetum compressum Species 0.000 claims description 6
- 235000014676 Phragmites communis Nutrition 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 4
- 240000003829 Sorghum propinquum Species 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 241001494508 Arundo donax Species 0.000 claims description 2
- 240000004784 Cymbopogon citratus Species 0.000 claims description 2
- 235000017897 Cymbopogon citratus Nutrition 0.000 claims description 2
- 241000594394 Hedyotis Species 0.000 claims description 2
- 241000510612 Imperatoria Species 0.000 claims description 2
- 235000015696 Portulacaria afra Nutrition 0.000 claims description 2
- 240000000111 Saccharum officinarum Species 0.000 claims description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 2
- 241001149258 Sporobolus alterniflorus Species 0.000 claims description 2
- 241000245565 Sporobolus anglicus Species 0.000 claims description 2
- 235000018747 Typha elephantina Nutrition 0.000 claims description 2
- 244000177175 Typha elephantina Species 0.000 claims description 2
- 239000004577 thatch Substances 0.000 claims description 2
- 241001434359 Muhlenbergia phleoides Species 0.000 claims 1
- 235000015503 Sorghum bicolor subsp. drummondii Nutrition 0.000 claims 1
- 244000170625 Sudangrass Species 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002028 Biomass Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002522 Wood fibre Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
本发明提供了一种利用能源草沼渣制备生物油的方法,该制备方法包括如下步骤:能源草厌氧沼气发酵处理、沼渣洗涤、沼渣烘干、沼渣粉碎、热裂解、热裂解蒸汽冷凝、加氢脱氧反应和加氢裂解反应等步骤。本发明利用沼气工程中排放的废弃物能源草沼渣生产商品化价值很高的生物油,是能源草沼渣在生物能源领域的进一步应用,可以使沼气工程的经济效益提高15%以上。
Description
技术领域
本发明属于生物质综合利用领域,具体涉及一种利用能源草沼渣制备生物油的方法。
背景技术
能源草包括一年生或多年生,高木质纤维素含量,高产量,高光合效率的草本能源植物,是开发潜力巨大的能源植物,已成为沼气工程的主要原料之一。能源草沼渣木质纤维素含量高,而且质地疏松,易于粉碎,适宜在生物能源领域进一步利用。能源草沼渣进一步高值化开发利用是提高沼气工程经济效益的重要途径。但是能源草沼渣一般做有机肥料直接排放到农田,经济效益不高。能源草沼渣可被生物降解利用的有效成分很低,不能通过生物发酵的方法经济高效地转化为生物能源,因此它在生物能源领域的进一步开发利用鲜有文献报道。
生物质热解是目前较有前景的生物质利用处置技术,可将低能量密度的生物质转化为高能量密度的气、液、固产品,其中热解得液态产物通常称为生物油。生物油一般有木料、锯末、农作物秸秆制备而成,因其原料结构致密,预处理过程复杂,且原料成分较为复杂,制备的生物油杂质较多,限制了其应用价值。
发明内容
本发明根据能源草沼渣性质开发出了一套完整高效的生物油生产技术,该方法包括以下具体步骤:
(1)把新鲜能源草、干燥能源草或青贮能源草粉碎到10厘米以下,进行厌氧沼气发酵,原料在发酵罐内滞留时间为中温35-40℃发酵18-45天或高温52℃-57℃发酵8~22天;
(2)发酵结束后,将发酵后的能源草沼渣排出,沥干沼液,沼渣浸泡在重量5~12倍的清水中洗涤3~5次,每次洗涤过程中搅拌3~8次,使能源草沼渣充分浸润,排出的沼液和洗涤液用于沼气发酵或能源草种植;
(3) 将洗涤后的能源草沼渣放入温度45~65℃、体积分数0.8~1.4%的乙酸溶液中,用20~90KHz超声处理20~50 分钟,然后取出沼渣,沥干乙酸溶液,再用清水洗涤3~5次。
(4)将步骤(3)清洗过的能源草沼渣沥干水分,自然晾晒至水分含量5~26wt%,然后在80℃~180℃烘干至含水率0.5~6wt%;
(5)用3000~6000转/分钟的高速切割粉碎机将干燥后的能源草沼渣粉碎至0.7厘米以下的细粉;
(6) 将所得的能源草沼渣细粉进行无氧热裂解,得到热裂解蒸汽,热裂解的方法为快速热裂解、闪速热裂解、真空热裂解和加氢热裂解中的一种;
(7)将所得的热裂解蒸汽通入冷凝器,在依次在20~50℃、10~20℃、-5~10℃、-20~-5℃四个冷凝梯度下冷却形成4种液体。
(8)对凝结的4种液体分别进行800~5000转/分钟离心,分离油相和水相;
(9)对4种油相分别采用Co-Mo或Ni-Mo做催化剂,在反应温度300~500 ℃、压力10~20 M Pa条件下,进行加氢脱氧反应和加氢裂解反应,进一步脱除残余的氧原子并降解大分子,得到直接用做燃料或与石化汽油、柴油混合使用的成品生物油。
所述能源草为杂交狼尾草、细茎杂交狼尾草、紫象草、矮象草、红象草、象草、牧草蔗、巨菌草、皇竹草、中国台湾甜草、拟高粱、甜高粱、芦竹、芦苇、类芦、斑茅、彼特草、苏丹草、美洲狼尾草、王草、五节芒、芒萁、香茅、互花米草, 大米草中的一种或几种。
步骤(6)所述快速热裂解工艺参数:升温速度12~20℃/s,反应温度590~760℃,原料滞留时间0.2~6s;闪速热裂解工艺参数:升温速度850~1500℃/s,反应温度500~680℃,原料滞留时间0.2~6s;真空热裂解工艺参数:升温速度1~10℃/s,反应温度250~420℃,原料滞留时间1~35s;加氢热裂解工艺参数:升温速度10~25℃/s,反应温度300~480℃,原料滞留时间0.5~8s。
相对于目前已有生产技术,本发明的优势在于:
(1)本发明根据沼气发酵的能源草沼渣灰分很低的特点,省去了常规原料中利用大量酸液脱灰分的步骤,大大节约了化学试剂的投入,节约了成本。
(2)能源草沼渣质地疏松,容易粉碎,本发明降低了粉碎机的耗电量,而且不需要汽爆等预处理步骤,节约了原料预处理过程中的能源投入。
(3)能源草沼渣木质纤维素含量高,纤维素、半纤维素、木质素比例合适,生产的生物油的不仅出油率高,而且生物油质量好。
(4)本发明利用沼气工程中排放的废弃物能源草沼渣生产商品化价值很高的生物油,是能源草沼渣在生物能源领域的进一步应用,可以使沼气工程的经济效益提高15%以上。
具体实施方式
以下结合具体实施例对本发明做进一步说明,但本发明不仅仅限于这些实施例。
实施例1
一种利用能源草沼渣制备生物油的方法,包括以下具体步骤:
(1)把新鲜能源草粉碎到10厘米以下,进行厌氧沼气发酵,原料在发酵罐内滞留时间为中温40℃发酵18天;
(2)发酵结束后,将发酵后的能源草沼渣排出,沥干沼液,沼渣浸泡在重量5倍的清水中洗涤3次,每次洗涤过程中搅拌3次,使能源草沼渣充分浸润,排出的沼液和洗涤液用于能源草种植;
(3) 将洗涤后的能源草沼渣放入温度45℃、体积分数0.8%的乙酸溶液中,用25KHz超声处理28 分钟,然后取出沼渣,沥干乙酸溶液,再用清水洗涤5次。
(4)将步骤(3)清洗过的能源草沼渣沥干水分,自然晾晒至水分含量16wt%,然后在180℃烘干至含水率1wt%;
(5)用3000转/分钟的高速切割粉碎机将干燥后的能源草沼渣粉碎至0.7厘米以下的细粉;
(6) 将所得的能源草沼渣细粉进行无氧热裂解,得到热裂解蒸汽,热裂解的方法为快速热裂解;
(7)将所得的热裂解蒸汽通入冷凝器,在依次在40℃、15℃、8℃、-12℃四个冷凝梯度下冷却形成4种液体。
(8)对凝结的4种液体分别进行1000转/分钟离心,分离油相和水相;
(9)对4种油相分别采用Co-Mo做催化剂,在反应温度300 ℃、压力10 M Pa条件下,进行加氢脱氧反应和加氢裂解反应,进一步脱除残余的氧原子并降解大分子,得到直接用做燃料或与石化汽油、柴油混合使用的成品生物油。
所述能源草为杂交狼尾草。
步骤(6)所述快速热裂解工艺参数:升温速度20℃/s,反应温度760℃,原料滞留时间0.2s。
实施例2
一种利用能源草沼渣制备生物油的方法,包括以下具体步骤:
(1)把干燥能源草粉碎到10厘米以下,进行厌氧沼气发酵,原料在发酵罐内滞留时间为高温52℃发酵18天;
(2)发酵结束后,将发酵后的能源草沼渣排出,沥干沼液,沼渣浸泡在重量7倍的清水中洗涤3次,每次洗涤过程中搅拌3次,使能源草沼渣充分浸润,排出的沼液和洗涤液用于沼气发酵;
(3) 将洗涤后的能源草沼渣放入温度65℃、体积分数0.8%的乙酸溶液中,用60KHz超声处理35 分钟,然后取出沼渣,沥干乙酸溶液,再用清水洗涤3次。
(4)将步骤(3)清洗过的能源草沼渣沥干水分,自然晾晒至水分含量12wt%,然后在100℃烘干至含水率3wt%;
(5)用3600转/分钟的高速切割粉碎机将干燥后的能源草沼渣粉碎至0.7厘米以下的细粉;
(6) 将所得的能源草沼渣细粉进行无氧热裂解,得到热裂解蒸汽,热裂解的方法为闪速热裂解;
(7)将所得的热裂解蒸汽通入冷凝器,在依次在25℃、15℃、0℃、-10℃四个冷凝梯度下冷却形成4种液体。
(8)对凝结的4种液体分别进行3000转/分钟离心,分离油相和水相;
(9)对4种油相分别采用Ni-Mo做催化剂,在反应温度500 ℃、压力12 M Pa条件下,进行加氢脱氧反应和加氢裂解反应,进一步脱除残余的氧原子并降解大分子,得到直接用做燃料或与石化汽油、柴油混合使用的成品生物油。
所述能源草为红象草。
步骤(6)所述闪速热裂解工艺参数:升温速度1500℃/s,反应温度680℃,原料滞留时间0.2s。
实施例3
一种利用能源草沼渣制备生物油的方法,包括以下具体步骤:
(1)把青贮能源草粉碎到10厘米以下,进行厌氧沼气发酵,原料在发酵罐内滞留时间为中温37℃发酵25天;
(2)发酵结束后,将发酵后的能源草沼渣排出,沥干沼液,沼渣浸泡在重量12倍的清水中洗涤3次,每次洗涤过程中搅拌3次,使能源草沼渣充分浸润,排出的沼液和洗涤液用于能源草种植;
(3) 将洗涤后的能源草沼渣放入温度55℃、体积分数1.2%的乙酸溶液中,用70KHz超声处理30 分钟,然后取出沼渣,沥干乙酸溶液,再用清水洗涤4次。
(4)将步骤(3)清洗过的能源草沼渣沥干水分,自然晾晒至水分含量26wt%,然后在180℃烘干至含水率6wt%;
(5)用3000~6000转/分钟的高速切割粉碎机将干燥后的能源草沼渣粉碎至0.7厘米以下的细粉;
(6) 将所得的能源草沼渣细粉进行无氧热裂解,得到热裂解蒸汽,热裂解的方法为真空热裂解;
(7)将所得的热裂解蒸汽通入冷凝器,在依次在50℃、20℃、10℃、-5℃四个冷凝梯度下冷却形成4种液体。
(8)对凝结的4种液体分别进行4500转/分钟离心,分离油相和水相;
(9)对4种油相分别采用Ni-Mo做催化剂,在反应温度450 ℃、压力18 M Pa条件下,进行加氢脱氧反应和加氢裂解反应,进一步脱除残余的氧原子并降解大分子,得到直接用做燃料或与石化汽油、柴油混合使用的成品生物油。
所述能源草为拟高粱。
步骤(6)所述真空热裂解工艺参数:升温速度10℃/s,反应温度420℃,原料滞留时间35s。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (2)
1.一种利用能源草沼渣制备生物油的方法,其特征在于,包括以下具体步骤:
(1)把新鲜能源草、干燥能源草或青贮能源草粉碎到10厘米以下,进行厌氧沼气发酵,原料在发酵罐内滞留时间为中温35-40℃发酵18-45天或高温52℃-57℃发酵8~22天;
(2)发酵结束后,将发酵后的能源草沼渣排出,沥干沼液,沼渣浸泡在重量5~12倍的清水中洗涤3~5次,每次洗涤过程中搅拌3~8次,使能源草沼渣充分浸润,排出的沼液和洗涤液用于沼气发酵或能源草种植;
(3)将洗涤后的能源草沼渣放入温度45~65℃、体积分数0.8~1.4%的乙酸溶液中,用20~90KHz超声处理20~50 分钟,然后取出沼渣,沥干乙酸溶液,再用清水洗涤3~5次;
(4)将步骤(3)清洗过的能源草沼渣沥干水分,自然晾晒至水分含量5~26wt%,然后在80℃~180℃烘干至含水率0.5~6wt%;
(5)用3000~6000转/分钟的高速切割粉碎机将干燥后的能源草沼渣粉碎至0.7厘米以下的细粉;
(6)将所得的能源草沼渣细粉进行无氧热裂解,得到热裂解蒸汽,热裂解的方法为快速热裂解、闪速热裂解、真空热裂解和加氢热裂解中的一种;
(7)将所得的热裂解蒸汽通入冷凝器,在依次在20~50℃、10~20℃、-5~10℃、-20~-5℃四个冷凝梯度下冷却形成4种液体;
(8)对凝结的4种液体分别进行800~5000转/分钟离心,分离油相和水相;
(9)对4种油相分别采用Co-Mo或Ni-Mo做催化剂,在反应温度300~500 ℃、压力10~20M Pa条件下,进行加氢脱氧反应和加氢裂解反应,进一步脱除残余的氧原子并降解大分子,得到直接用做燃料或与石化汽油、柴油混合使用的成品生物油;
所述能源草为杂交狼尾草、细茎杂交狼尾草、紫象草、矮象草、红象草、象草、牧草蔗、巨菌草、皇竹草、台湾甜草、拟高粱、甜高粱、芦竹、芦苇、类芦、斑茅、彼特草、苏丹草、美洲狼尾草、王草、五节芒、芒萁、香茅、互花米草、 大米草中的一种或几种。
2.根据权利要求书1所述的一种利用能源草沼渣制备生物油的方法,其特征在于:
步骤(6)所述快速热裂解工艺参数:升温速度12~20℃/s,反应温度590~760℃,原料滞留时间0.2~6s;闪速热裂解工艺参数:升温速度850~1500℃/s,反应温度500~680℃,原料滞留时间0.2~6s;真空热裂解工艺参数:升温速度1~10℃/s,反应温度250~420℃,原料滞留时间1~35s;加氢热裂解工艺参数:升温速度10~25℃/s,反应温度300~480℃,原料滞留时间0.5~8s。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710041910.8A CN106811227B (zh) | 2017-01-20 | 2017-01-20 | 一种利用能源草沼渣制备生物油的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710041910.8A CN106811227B (zh) | 2017-01-20 | 2017-01-20 | 一种利用能源草沼渣制备生物油的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106811227A CN106811227A (zh) | 2017-06-09 |
CN106811227B true CN106811227B (zh) | 2018-09-18 |
Family
ID=59111404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710041910.8A Expired - Fee Related CN106811227B (zh) | 2017-01-20 | 2017-01-20 | 一种利用能源草沼渣制备生物油的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106811227B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108856261A (zh) * | 2018-06-21 | 2018-11-23 | 湖南双晟科技信息咨询有限公司 | 一种餐厨垃圾综合处理方法 |
CN108998065A (zh) * | 2018-08-06 | 2018-12-14 | 安徽上元新型家居材料有限公司 | 一种秸秆生物质油及其制备工艺 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101914572B (zh) * | 2010-07-20 | 2012-07-25 | 中国科学院广州能源研究所 | 二氧化碳零排放型有机废弃物能源化利用的方法 |
CN102277188B (zh) * | 2011-07-25 | 2014-06-18 | 青岛福瑞斯生物能源科技开发有限公司 | 生物质热裂解液化燃用油技术 |
CN102808000B (zh) * | 2012-08-23 | 2014-06-25 | 辽宁科技大学 | 城市生活垃圾资源化分级利用及固碳处理方法 |
CN103088070B (zh) * | 2013-01-22 | 2015-05-13 | 北京化工大学 | 一种农作物秸秆与畜禽粪便联合固态发酵生产沼气的方法 |
CN103088073A (zh) * | 2013-02-04 | 2013-05-08 | 北京化工大学 | 一种厌氧消化耦合热解技术处理食醋工业废弃物的方法 |
CN103265968A (zh) * | 2013-06-04 | 2013-08-28 | 北京林业大学 | 一种基于综合热解的高值生物油制备方法 |
-
2017
- 2017-01-20 CN CN201710041910.8A patent/CN106811227B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN106811227A (zh) | 2017-06-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ferreira et al. | Biomethane potential of wheat straw: influence of particle size, water impregnation and thermal hydrolysis | |
Bala et al. | Development of an environmental-benign process for efficient pretreatment and saccharification of Saccharum biomasses for bioethanol production | |
Zhang et al. | Comparison of various pretreatments for ethanol production enhancement from solid residue after rumen fluid digestion of rice straw | |
Niju et al. | Delignification of sugarcane bagasse using pretreatment strategies for bioethanol production | |
CN100365099C (zh) | 全新的生物质生产液体燃料技术 | |
Song et al. | Improving biohydrogen production through dark fermentation of steam-heated acid pretreated Alternanthera philoxeroides by mutant Enterobacter aerogenes ZJU1 | |
Li et al. | Enhanced biomethane production from Miscanthus lutarioriparius using steam explosion pretreatment | |
AU2009285815A1 (en) | Materials and methods for converting biomass to biofuel | |
US11618861B2 (en) | Cellulosic biofuel | |
US8852301B1 (en) | Composition of lignin pellets and system for producing | |
JP2010508390A (ja) | バイオマスの加工方法 | |
UA119796C2 (uk) | Спосіб обробки матеріалу біомаси й органічних відходів | |
CN110358599B (zh) | 一种基于水热反应的农林废弃物脱碱炭化方法 | |
Kaur et al. | Effect of chemical pretreatment of sugarcane bagasse on biogas production | |
Mechery et al. | Biohydrogen production from acidic and alkaline hydrolysates of paddy straw using locally isolated facultative bacteria through dark fermentation | |
CA2978347C (en) | Cellulosic biofuel and co-products | |
Wang et al. | Efficient ethanol production from paper mulberry pretreated at high solid loading in Fed-nonisothermal-simultaneous saccharification and fermentation | |
CN104690068B (zh) | 一种利用生物质制备水热焦的方法 | |
Kassim et al. | Bioprocessing of sustainable renewable biomass for bioethanol production | |
CN106811227B (zh) | 一种利用能源草沼渣制备生物油的方法 | |
CN106755126A (zh) | 一种利用能源草沼渣制备生物碳的方法 | |
CN105039421B (zh) | 一种玉米秸秆沼气制备耦合发电余热利用的方法 | |
Karami et al. | Mesophilic aerobic digestion: An efficient and inexpensive biological pretreatment to improve biogas production from highly-recalcitrant pinewood | |
Mechery et al. | Biohydrogen production by locally isolated facultative bacterial species using the biomass of Eichhornia crassipes: effect of acid and alkali treatment | |
Wu et al. | Microwave pretreatments of switchgrass leaf and stem fractions to increase methane production |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180918 |