CN113755250B - 一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺 - Google Patents
一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺 Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000007787 solid Substances 0.000 title claims abstract description 58
- 239000003225 biodiesel Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000006227 byproduct Substances 0.000 title claims abstract description 12
- 239000010426 asphalt Substances 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000011358 absorbing material Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 23
- 238000002309 gasification Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 14
- 238000005809 transesterification reaction Methods 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- VPWAVWZPVGDNMN-UHFFFAOYSA-L calcium;2,3-dihydroxypropanoate Chemical group [Ca+2].OCC(O)C([O-])=O.OCC(O)C([O-])=O VPWAVWZPVGDNMN-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- JNPQFTCBVDSMDO-UHFFFAOYSA-L zinc;2,3-dihydroxypropanoate Chemical compound [Zn+2].OCC(O)C([O-])=O.OCC(O)C([O-])=O JNPQFTCBVDSMDO-UHFFFAOYSA-L 0.000 claims description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- PIXWOIFHSZAPGV-UHFFFAOYSA-L magnesium;2,3-dihydroxypropanoate Chemical compound [Mg+2].OCC(O)C([O-])=O.OCC(O)C([O-])=O PIXWOIFHSZAPGV-UHFFFAOYSA-L 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 9
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- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- LRGQZEKJTHEMOJ-UHFFFAOYSA-N propane-1,2,3-triol;zinc Chemical compound [Zn].OCC(O)CO LRGQZEKJTHEMOJ-UHFFFAOYSA-N 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 5
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 5
- 150000004702 methyl esters Chemical class 0.000 description 5
- 235000021314 Palmitic acid Nutrition 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- QHZLMUACJMDIAE-SFHVURJKSA-N 1-hexadecanoyl-sn-glycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)CO QHZLMUACJMDIAE-SFHVURJKSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229940096898 glyceryl palmitate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10J2300/00—Details of gasification processes
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- C10J2300/0983—Additives
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- C10J2300/00—Details of gasification processes
- C10J2300/12—Heating the gasifier
- C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves
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Abstract
本发明公开了一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,它将粗甘油进行精馏回收甘油,精馏残余物即为含有固体碱催化剂的甘油沥青,随后将甘油沥青与气化剂一并通入至反应器内的吸波材料床层表面,在微波辐射加热至气化温度700~1100℃下进行气化反应;反应所得气体产物是以一氧化碳与氢气为主要成分的合成气产品,气化反应的过程中固体碱催化剂以固体的形式析出沉积在吸波材料床层表面,将吸波材料上积留的固体颗粒筛分下来收集进行回收。本发明所述的方法可实现固体碱催化剂的回收利用,降低生物柴油生产成本;同时可以将沥青转化为高品质合成气,实现沥青的资源化利用,从而能够提高生物柴油企业的经济效益和环境效益。
Description
技术领域
本发明涉及一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺。
背景技术
生物柴油具有无污染、生物可降解、燃烧性能好等优点,是一种应用前景广阔的绿色能源。生物柴油的制备方法包括均相催化法、非均相催化法、酶催化法等。其中,非均相固体碱催化酯交换制备生物柴油有利于催化剂的回收利用,并且可以有效减少皂化和酸性废水的产生,具有良好的工业化前景。常用的固体碱催化剂包括氧化钙、氧化镁、氧化锌等金属氧化物,然而此类催化在酯交换反应中会与甘油反应转化为相应的甘油基催化剂(甘油钙、甘油镁、甘油锌等),在反应中起主要催化作用。酯交换反应后,甘油会大量附着在甘油基固体催化剂上,且部分甘油基催化剂会溶于甘油中,从而很难通过简单的过滤或离心等操作实现催化剂的回收利用。另外,甘油基催化剂在甘油精馏后会残留在甘油沥青中,进一步增加了催化剂的回收难度。
中国专利CN 101913638 A制备了一种微米氧化钙并用于生物柴油的制备,可以获得较高的生物柴油产率。中国专利CN 104946407 A将煅烧的壳类(主要成分是氧化钙)用作生物柴油催化剂,并在生产过程中得到了甘油钙产品。但是,上述固体碱催化生物柴油的制备方法都未考虑催化剂的回收利用。
甘油沥青中除了残留的甘油基催化剂,还含有甘油、聚合甘油、胶质等有机物。这些有机物可以在高温气化条件下彻底去除,而甘油基催化剂在气化过程中则可以转化为初始的金属氧化物,从而实现催化剂的回收利用。然而,由于甘油沥青热值较低且难以直接利用,目前工业上常作为危废处置,造成资源浪费和环境污染,且影响催化剂的回收。
发明内容
本发明的目的在于克服现有技术存在的不足,提供一种生物柴油固体催化剂的回收方法,该方法在实现催化剂回收利用的同时可以实现甘油沥青的资源化处理,从而能够提高生物柴油企业的经济效益和环境效益。
所述的一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于所述粗甘油是由以下方法制备而得:甲醇与甘油酯经固体碱催化剂催化酯交换反应制备生物柴油,反应结束后,旋蒸脱除甲醇,静置分层,下层混合液即为含有固体碱催化剂的粗甘油;所述固体碱催化剂为甘油钙、甘油镁或甘油锌;
所述含固体碱催化剂的粗甘油的处理工艺包括以下步骤:
1)将粗甘油进行精馏回收甘油,精馏至釜液的甘油质量含量在15%以下,精馏残余物即为含有固体碱催化剂的甘油沥青;
2)对步骤1)所得含有固体碱催化剂的甘油沥青进行热处理,过程为:将填充有吸波材料的反应器置于微波发生装置中进行微波辐射加热升温,待吸波材料床层升温至气化温度700~1100℃时,将含有固体碱催化剂的甘油沥青原料通入至反应器内的吸波材料床层表面,同时向反应器内通入气化剂,进行气化反应;反应所得气体产物通过旋风分离后,冷却分离出水分,即获得以一氧化碳与氢气为主要成分的合成气产品,气化反应的过程中固体碱催化剂以金属氧化物固体的形式析出沉积在吸波材料床层表面,当床层表面积留一层金属氧化物固体颗粒时,终止反应并取出反应器内的吸波材料,将吸波材料上积留的固体颗粒筛分下来,即回收得到高纯金属氧化物;回收的高纯金属氧化物重新与甘油反应,即可制得所述固体碱催化剂。
所述的一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于:所述吸波材料为碳化硅、钛化硅、铁氧体中的一种或几种,粒径范围为1~3 mm。
所述的一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于:所述气化温度750-900℃。
所述的一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于:所述气化剂为空气、氧气或水蒸气,气化剂与甘油沥青的进料质量比为1:1~3:1。
所述的一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于:精馏残余物甘油沥青中,各组分的质量含量为:甘油10~15%,胶质15~20%,固体碱催化剂1~5%,其余为聚合甘油。
所述的一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于:步骤2)中,以甘油沥青原料中的有机物成分计,最终所得合成气产品的质量产率达70%以上,且所得合成气产品中的一氧化碳与氢气两者的总体积含量在60%以上。
通过采用上述技术,与现有技术相比,本发明的有益效果为:
1)利用气化技术处理含有固体碱催化剂的沥青原料,可以实现固体碱催化剂的回收利用,降低生物柴油生产成本;同时可以将沥青转化为高品质合成气,实现沥青的资源化利用,从而能够提高生物柴油企业的经济效益和环境效益。
2)本发明中需要回收的固体碱催化剂不仅可以催化酯交换反应,而且在气化反应中可以促进焦油裂解和重整生成小分子气体,还能够促进水煤气变换反应(CO+H2O↔CO2+H2)朝正向移动,从而提高合成气的产率和品质。
3)本发明利用微波加热进行沥青气化实现固体碱催化剂的回收,其生产效率高、能耗低且生产过程绿色化,加之微波装置具有小型化、易于控制等优点,因而此方法适于推广应用。
具体实施方案
下面结合具体实施事例对本发明作进一步说明,但本发明的保护范围并不限于此。
实施例1:
在实施例1中,氧化钙固体与甘油在甲醇中反应制备甘油钙催化剂,反应温度60℃,反应时间为4h,氧化钙、甘油与甲醇的摩尔比为1:12:10,后续通过离心烘干即可得到甘油钙固体。
将棕榈酸甘油酯、甲醇以及上述制备的甘油钙三者混合,形成的反应液持续搅拌,搅拌速度600 r/min。其中反应液中,甲醇的总用量为棕榈酸甘油酯质量的40wt%、催化剂甘油钙的用量为棕榈酸甘油酯质量的1 wt%。在60℃温度、搅拌速度600 r/min下反应4h后,旋蒸脱除甲醇,随后静置分层,下层混合液进行甘油精馏后得到含有甘油钙催化剂的甘油沥青。酯交换反应的甲酯收率为96%,得到的甘油沥青组成的质量含量为:甘油钙5%、甘油10%、胶质20%,其余为聚合甘油。
将粒径为1 mm左右的SiC吸波材料放于反应器中作为高温气化床层,将反应器置于微波发生装置中,开启微波发生装置,对反应器中的SiC吸波材料进行加热升温。待SiC床层温度升至750℃后,将上述制备的含有甘油钙的甘油沥青原料通入至反应器内的SiC床层表面,同时向反应器内通入气化剂水蒸气,使甘油沥青原料与水蒸气按质量比为1:1在反应器内进行气化反应。当反应器内床层表面积留一层固体颗粒时,停止反应并将反应器中的SiC材料取出,并将SiC上的固体颗粒筛分下来进行收集,即回收得到氧化钙,回收的氧化钙重新与甘油在甲醇中反应即可再次得到甘油钙催化剂;反应所得的气体产物通过旋风分离器分离后,冷却至40~50℃使得其中的水分冷凝下来,即获得合成气产品。
本实施例中回收得到的氧化钙纯度可达90%以上。以甘油沥青原料中的有机物成分计,最终合成气产品的质量产率可达72%,合成气中氢气和一氧化碳的总体积含量可达65%。将回收得到的氧化钙制备甘油钙后用于催化酯交换反应,相同反应条件下可得甲酯收率为94%,与新鲜催化剂催化效果相当。
实施例2:
在实施例2中,氧化锌固体与甘油反应制备甘油锌催化剂,反应温度160℃,反应时间为8h,氧化锌与甘油的质量比为1:10,后续通过过滤烘干即可得到甘油锌固体。
将棕榈酸甘油酯、甲醇以及上述制备的甘油锌三者混合,形成的反应液持续搅拌,搅拌速度600 r/min。其中反应液中,甲醇的总用量为棕榈酸甘油酯质量的40 wt%、催化剂甘油锌的用量为棕榈酸甘油酯质量的1 wt%。在60℃温度、搅拌速度600 r/min下反应4h后,旋蒸脱除甲醇,随后静置分层,下层混合液进行甘油精馏后得到含有甘油锌催化剂的甘油沥青。酯交换反应的甲酯收率为92%,得到的甘油沥青组成的质量含量为:甘油锌4%、甘油10%、胶质20%,其余为聚合甘油。
将粒径为1.5 mm左右的SiC吸波材料放于反应器中作为高温气化床层,将反应器置于微波发生装置中,开启微波发生装置,对反应器中的SiC吸波材料进行加热升温。待SiC床层温度升至900℃后,将上述制备的含有甘油锌的沥青原料通入至反应器内的SiC床层表面,同时向反应器内通入气化剂水蒸气,使沥青原料与水蒸气按质量比为1:2在反应器内进行气化反应。当反应器内床层表面积留一层固体颗粒时,停止反应并将反应器中的SiC材料取出,并将SiC上的固体颗粒筛分下来进行收集,即回收得到氧化锌,回收的氧化锌重新与甘油反应即可再次得到甘油锌催化剂;反应所得的气体产物通过旋风分离器分离后,冷却至40~50℃使得其中的水分冷凝下来,即获得合成气产品。
本实施例中回收得到的氧化锌纯度可达90%以上。以甘油沥青原料中的有机物成分计,最终合成气产品的质量产率可达82%,合成气中氢气和一氧化碳的总体积含量可达73%。将回收得到的氧化锌制备甘油锌后用于催化酯交换反应,相同反应条件下可得甲酯收率为91%,与新鲜催化剂催化效果相当。
实施例3:
在实施例3中,将棕榈酸甘油酯在温度60℃、搅拌速度600 r/min、甲醇用量为棕榈酸甘油酯质量的40 wt%、催化剂氢氧化钾用量为棕榈酸甘油酯质量的1 wt%下反应1h后,旋蒸脱除甲醇,随后静置分层,下层混合液进行甘油精馏后得到含有氢氧化钾催化剂的甘油沥青。酯交换反应的甲酯收率为94%,得到的甘油沥青组成的质量含量为:甘油10%、胶质20%,氢氧化钾5%,其余为聚合甘油。
将粒径为1 mm左右的SiC吸波材料放于反应器中作为高温气化床层,将反应器置于微波发生装置中,开启微波发生装置,对反应器中的SiC吸波材料进行加热升温。待SiC床层温度升至750℃后,将上述制备的含有氢氧化钾的沥青原料通入至反应器内的SiC床层表面,同时向反应器内通入气化剂水蒸气,使沥青原料与水蒸气按质量比为1:1在反应器内进行气化反应,反应所得的气体产物通过旋风分离器分离后,冷却至40~50℃使得其中的水分冷凝下来,即获得合成气产品。
本实施例中以甘油沥青原料中的有机物成分计,最终合成气产品的质量产率可达62%,合成气中氢气和一氧化碳的总体积含量可达54%。
本说明书所述的内容仅仅是对发明构思实现形式的列举,本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式。
Claims (2)
1.一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于所述粗甘油是由以下方法制备而得:甲醇与甘油酯经固体碱催化剂催化酯交换反应制备生物柴油,反应结束后,旋蒸脱除甲醇,静置分层,下层混合液即为含有固体碱催化剂的粗甘油;所述固体碱催化剂为甘油钙、甘油镁或甘油锌;
所述含固体碱催化剂的粗甘油的处理工艺包括以下步骤:
1)将粗甘油进行精馏回收甘油,精馏至釜液的甘油质量含量在15%以下,精馏残余物即为含有固体碱催化剂的甘油沥青;
2)对步骤1)所得含有固体碱催化剂的甘油沥青进行热处理,过程为:将填充有吸波材料的反应器置于微波发生装置中进行微波辐射加热升温,待吸波材料床层升温至气化温度750~900℃时,将含有固体碱催化剂的甘油沥青原料通入至反应器内的吸波材料床层表面,同时向反应器内通入气化剂,进行气化反应;反应所得气体产物通过旋风分离后,冷却分离出水分,即获得以一氧化碳与氢气为主要成分的合成气产品,气化反应的过程中固体碱催化剂以金属氧化物固体的形式析出沉积在吸波材料床层表面,当床层表面积留一层金属氧化物固体颗粒时,终止反应并取出反应器内的吸波材料,将吸波材料上积留的固体颗粒筛分下来,即回收得到高纯金属氧化物;回收的高纯金属氧化物重新与甘油反应,即可制得所述固体碱催化剂;
精馏残余物甘油沥青中,各组分的质量含量为:甘油10~15%,胶质15~20%,固体碱催化剂1~5%,其余为聚合甘油;
所述气化剂为水蒸气,气化剂与甘油沥青的进料质量比为1:1~3:1;
步骤2)中,以甘油沥青原料中的有机物成分计,最终所得合成气产品的质量产率达70%以上,且所得合成气产品中的一氧化碳与氢气两者的总体积含量在60%以上。
2.如权利要求1所述的一种生物柴油副产含固体碱催化剂的粗甘油的处理工艺,其特征在于:所述吸波材料为碳化硅、钛化硅、铁氧体中的一种或几种,粒径范围为1~3mm。
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