CN109663585A - 一种固体碱催化剂的制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000007787 solid Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 13
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000001110 calcium chloride Substances 0.000 claims abstract description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004113 Sepiolite Substances 0.000 claims abstract description 8
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- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- PLGPSDNOLCVGSS-UHFFFAOYSA-N Tetraphenylcyclopentadienone Chemical compound O=C1C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PLGPSDNOLCVGSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
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- 229910052749 magnesium Inorganic materials 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
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- 239000011148 porous material Substances 0.000 abstract description 4
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- 230000000694 effects Effects 0.000 abstract description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 238000006243 chemical reaction Methods 0.000 description 6
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- 235000011147 magnesium chloride Nutrition 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
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- 239000002994 raw material Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000019737 Animal fat Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000299507 Gossypium hirsutum Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
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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
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Abstract
本发明涉及一种固体碱催化剂的制备方法,其特征是制备方法包括以下步骤:1)将废催化剂、海泡石加入到酸性溶液中,室温下浸渍3‑24 h;2)将氯化钙、硝酸钙、氯化镁、硝酸镁中的一种或几种加入到步骤1)中,混合均匀,加入碱性溶液,搅拌反应0.5‑2h,之后加入可溶性硅酸盐,混合均匀,过滤,滤饼在500‑900℃下焙烧0.5‑10 h,冷却,研磨至100‑200目的颗粒产品。本发明的固体碱催化剂比表面积和孔体积较大,含有丰富的中大孔结构,活性及稳定性高,具有良好的抗磨损性能,催化剂便于分离回收,可重复使用。
Description
技术领域
本发明涉及一种固体碱催化剂的制备方法,特别是涉及一种制备生物柴油的固体碱催化剂的制备方法,属于催化剂制备的技术领域。
背景技术
随着全球性石油资源的日益枯竭和社会发展对能源需求的不断增加,能源短缺已成为世界性问题。从能源战略和环境保护的角度出发,世界各国都在积极开展石化燃料替代品的研究,其中以生物柴油的研究为当前热点。生物柴油是指以油料作物如大豆、油菜、棉、棕榈等,野生油料植物和工程微藻等水生植物油脂以及动物油脂、餐饮垃圾油等为原料油制成的可再生新型燃料。目前国内外应用最广泛的生物柴油的制备方法是酯交换法,有均相酸碱催化和非均相固体酸碱催化两种工艺。均相酸碱催化具有反应速度快、转化率高的优点,其弊端在于催化剂难以回收重复利用,产品的中和洗涤会产生大量的工业废水,容易造成环境污染,同时后处理复杂,给副产物甘油的分离、精制造成困难。
由于固体酸催化过程中不可避免地发生碳化现象,影响产品收率,相比而言,固体碱催化反应更具优势。目前已经发展形成了多种类型的固体碱催化体系。在常用固体碱催化剂中,负载型固体碱催化剂因其制备简单、比表面积相对较大、碱性强和孔径均匀等优点而成为最受欢迎的一种催化剂。用作催化剂载体的材料多为:Al2O3、CaO、活性碳等,这类载体的主要特点是内部多孔,具有较大的比表面积,可以较好的起到分散作用。
氧化钙和氧化镁等固体碱催化剂可有效催化酯交换反应,可用于生产生物柴油,但氧化钙和氧化镁等组分在制备过程中容易烧结和团聚,导致比表面积小,催化活性位难以有效暴露和充分利用,影响催化活性,且氧化钙和氧化镁的机械强度和稳定性差,在酯交换反应快速混合过程中会有部分破碎或水解,形成悬浮液,使反应完成后催化剂分离困难。因此,氧化钙和氧化镁固体碱催化剂的比表面低,难以分散,机械强度和稳定性差成为其应用必需解决的问题。
发明内容
本发明的目的是提供一种工艺简单、成本低廉、催化活性高、寿命长的用于制备生物柴油的固体碱催化剂的制备方法。
本发明以废催化剂和海泡石为主要原料,采用浸渍、焙烧和成型的方法制备用于生产生物柴油的固体碱催化剂。成品催化剂的比表面在100-200 m2/g,拥有发达的中大孔结构,具有很好的抗磨损性能,可以保证催化剂对材料强度和孔道的要求。该制备方法的特征在于以下步骤:
1)将废催化剂、海泡石加入到酸性溶液中,室温下浸渍3-24 h;
2)将氯化钙、硝酸钙、氯化镁、硝酸镁中的一种或几种加入到步骤 1)中,混合均匀,加入碱性溶液,搅拌反应0.5-2 h,之后加入可溶性硅酸盐,混合均匀,过滤,滤饼在500-900℃下焙烧0.5-10 h,冷却,研磨至100-200 目的颗粒产品。
2、根据权利要求1所述的方法,其特征在于步骤1)所述的废催化剂为催化裂化废催化剂、催化裂化装置上三级、四级旋风分离器和烟道气中的废催化剂细粉中的一种或几种。
3、根据权利要求1所述的方法,其特征在于步骤1)所述的酸性溶液为硫酸、硝酸、盐酸、草酸、乙酸中的一种或几种,酸性溶液的浓度为 5-50 %,其加入量为废催化剂与海泡石总重量的50-300 %。
4、根据权利要求1所述的方法,其特征在于步骤1)所述的废催化剂的加入量为废催化剂与海泡石总重量的30-70 %。
5、根据权利要求1所述的方法,其特征在于步骤2)所述的碱性溶液为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、磷酸钠、醋酸钠、偏铝酸钠中的一种或几种,碱性溶液的浓度为10-30 %,其加入量为步骤1)和2)中固体总重量的100-300 %。
6、根据权利要求1所述的方法,其特征在于步骤2)所述的氯化钙、硝酸钙、氯化镁、硝酸镁中的一种或几种的加入量为步骤1)和2)中固体总重量的10-30 %。
7、根据权利要求1所述的方法,其特征在于步骤2)所述的可溶性硅酸盐为硅酸钠、硅酸钾中的一种或几种,其加入量为步骤1)和2)中固体总重量的1-10 %。
本发明与已有技术相比具有以下优点:
(1)本发明的固体碱催化剂是采用废催化剂和天然矿物海泡石为主要原料制备而成的,通过酸改性,在保持和改善其孔道结构的基础上有效去除杂质成分,提供了丰富的中大孔结构和大的比表面积和孔体积,活性组分分布均匀,催化剂具有高的活性及稳定性;其次通过后改性强化了催化剂的抗磨损能力,克服了单纯氧化钙和氧化镁等固体碱催化剂在应用过程中机械强度和稳定性差的问题。
(2)本发明克服了碱催化制备过程存在的产物分离困难,设备易腐蚀,产生大量废水,污染环境等缺点,催化剂的制备方法简便,原料适应性较强。
(3)本发明的固体碱催化剂用于生物柴油制备,其产率和纯度高,催化剂用量较小,反应条件温和,反应时间短,催化剂可重复使用。
(4)本发明可深层次的利用固体废料,降低生产成本,减少炼油厂固体废料,减少环境污染,可实现固体废弃物的高效回收及利用,具有更大的社会效益和经济效益。
具体实施方式
下面结合实施例对本发明作进一步详细说明,但并不因此限制本发明。
实施例1
1)将100 gFCC装置旋风分离器收集的废催化剂细粉、275 g海泡石加入到335 g、5 %的硫酸溶液中,室温下浸渍24 h;2)将23 g氯化钙、10 g氯化镁加入到步骤 1)中,混合均匀,加入15 %的氢氧化钠溶液350 g,搅拌反应0.5 h,之后加入4 g硅酸钠,混合均匀,过滤,滤饼在600 ℃下焙烧 7 h,冷却,研磨至100-200目的颗粒产品。制得催化剂 A。
实施例2
1)将25 gFCC废催化剂、30 g海泡石加入到75 g 的20 %的盐酸溶液中,室温下浸渍6h;2)将7.5 g 硝酸钙、7.5 g 硝酸镁加入到步骤 1)中,混合均匀,加入29 %的偏铝酸钠溶液190 g,搅拌反应2 h,之后加入3.5 g硅酸钾,混合均匀,过滤,滤饼在900 ℃下焙烧0.5h,冷却,研磨至100-200 目的颗粒产品。制得催化剂 B。
实施例3
1)将20 gFCC废催化剂、12 g海泡石加入到45 g的50 %的磷酸溶液中,室温下浸渍12h;2)将6 g氯化钙加入到步骤 1)中,混合均匀,加入18 %的碳酸钾溶液53 g,搅拌反应1 h,之后加入2 g硅酸钠,混合均匀,过滤,滤饼在500 ℃下焙烧10 h,冷却,研磨至100-200目的颗粒产品。制得催化剂 C。
实施例4
1)将126 gFCC废催化剂、80 g海泡石加入到200 g 的25 %的草酸溶液中,室温下浸渍16 h;2)将将15 g氯化钙、28 g氯化镁加入到步骤 1)中,混合均匀,加入30 %的碳酸钠溶液300 g,搅拌反应1 h,之后加入 16 g硅酸钠,混合均匀,过滤,滤饼在750 ℃下焙烧 3.5 h,冷却,研磨至100-200目的颗粒产品。制得催化剂 D。
实施例5
1)将28 gFCC装置的废催化剂细粉、61 g海泡石加入到105 g的35 %的醋酸溶液中,室温下浸渍8 h;2)将8 g氯化钙、7 g氯化镁加入到步骤 1)中,混合均匀,加入33 %的氢氧化钠溶液95 g,搅拌反应1.5 h,之后加入3 g硅酸钾,混合均匀,过滤,滤饼在800 ℃下焙烧2h,冷却,研磨至100-200目的颗粒产品。制得催化剂 E。
实施例6
催化剂的活性测试,在三口烧瓶、搅拌器、回流冷凝管等组成的反应装置中进行反应,加入大豆油30 g、甲醇18 mL、催化剂3 g,升温至55-65 ℃反应2-6 h。反应结束后过滤除去催化剂,将滤液倒入分液漏斗中,分为上下层,倒出上层油相,水浴蒸馏除去甲醇,得到生物柴油,将下层中剩余甲醇蒸出,得甘油相,计算产率。实验结果见表1。对催化剂A进行寿命考察,实验结果见表2。结果显示,催化剂具有活性高和寿命长的特点。
Claims (7)
1.一种固体碱催化剂的制备方法,其特征是制备方法包括以下步骤:
1)将废催化剂、海泡石加入到酸性溶液中,室温下浸渍3-24 h;
2)将氯化钙、硝酸钙、氯化镁、硝酸镁中的一种或几种加入到步骤 1)中,混合均匀,加入碱性溶液,搅拌反应0.5-2 h,之后加入可溶性硅酸盐,混合均匀,过滤,滤饼在500-900℃下焙烧0.5-10 h,冷却,研磨至100-200 目的颗粒产品。
2.根据权利要求1所述的方法,其特征在于步骤1)所述的废催化剂为催化裂化废催化剂、催化裂化装置上三级、四级旋风分离器和烟道气中的废催化剂细粉中的一种或几种。
3.根据权利要求1所述的方法,其特征在于步骤1)所述的酸性溶液为硫酸、硝酸、盐酸、草酸、乙酸中的一种或几种,酸性溶液的浓度为 5-50 %,其加入量为废催化剂与海泡石总重量的50-300 %。
4.根据权利要求1所述的方法,其特征在于步骤1)所述的废催化剂的加入量为废催化剂与海泡石总重量的30-70 %。
5.根据权利要求1所述的方法,其特征在于步骤2)所述的碱性溶液为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、磷酸钠、醋酸钠、偏铝酸钠中的一种或几种,碱性溶液的浓度为10-30%,其加入量为步骤1)和2)中固体总重量的100-300 %。
6.根据权利要求1所述的方法,其特征在于步骤2)所述的氯化钙、硝酸钙、氯化镁、硝酸镁中的一种或几种的加入量为步骤1)和2)中固体总重量的10-30 %。
7.根据权利要求1所述的方法,其特征在于步骤2)所述的可溶性硅酸盐为硅酸钠、硅酸钾中的一种或几种,其加入量为步骤1)和2)中固体总重量的1-10 %。
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