CN106944112B - Pre-esterification solid acid catalyst for high-acid-value waste oil - Google Patents
Pre-esterification solid acid catalyst for high-acid-value waste oil Download PDFInfo
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- CN106944112B CN106944112B CN201710157289.1A CN201710157289A CN106944112B CN 106944112 B CN106944112 B CN 106944112B CN 201710157289 A CN201710157289 A CN 201710157289A CN 106944112 B CN106944112 B CN 106944112B
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- esterification
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000002253 acid Substances 0.000 title claims abstract description 66
- 239000011973 solid acid Substances 0.000 title claims abstract description 56
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 53
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 230000032050 esterification Effects 0.000 claims abstract description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052593 corundum Inorganic materials 0.000 claims description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 22
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 15
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 14
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 14
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000004519 grease Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005696 Diammonium phosphate Substances 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 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 2
- 239000002440 industrial waste Substances 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- -1 M-salt Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000011156 evaluation Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 34
- 235000019198 oils Nutrition 0.000 description 34
- 239000003225 biodiesel Substances 0.000 description 9
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229940013123 stannous chloride Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
-
- B01J35/30—
-
- 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
Abstract
The invention discloses synthesis and application of a solid acid catalyst, and particularly relates to a solid acid catalyst for pre-esterification of waste oil with a high acid value, and a preparation method and a use method thereof2O3Wherein M can be one or more of Co, Ni, Sn and Sb. The preparation method of the solid acid catalyst comprises the following steps: and (3) placing the alumina into the prepared mixed solution twice, soaking, drying and calcining to prepare the solid acid catalyst. The solid acid catalyst has no corrosion to the reaction equipment and is easily separated from the reaction product. The catalyst can be repeatedly used after being activated, and the catalytic activity is not obviously reduced after 10 times of repeated use. The catalytic activity is good after 120 hours of continuous evaluation, and the method has good industrial application prospect particularly for pre-esterification of high-acid-value waste oil.
Description
Technical Field
The invention belongs to the technical field of novel environment-friendly catalysts, and particularly relates to a solid acid catalyst for pre-esterification of high-acid-value waste oil and a preparation method and a use method thereof.
Background
The problems of the over-exploitation and utilization of petroleum resources, such as the high price and the increasing shortage thereof, are receiving more and more attention. The search for new alternative energy sources has become a hot topic in the world today. As a sustainable clean energy, the biodiesel has excellent environmental protection property, low emission of sulfur dioxide and sulfide in combustion products, renewability, economy and good safety performance, is a novel green and environmental-friendly energy, but has the problems of high raw material cost, serious pollution and corrosion of a liquid acid catalyst used for production and the like in the preparation of the biodiesel. Therefore, reducing the cost of raw materials and developing new environmentally friendly catalysts are important approaches to the problem.
The high acid value waste grease ester has higher initial acid value, and if the high acid value waste grease ester is directly used for preparing biodiesel by exchange, the high acid value waste grease ester can cause the poisoning and inactivation of an alkaline catalyst due to over high acid value. Therefore, before the high acid value waste oil is used, the raw material needs to be subjected to pre-esterification reaction, the acid value of the high acid value waste oil is reduced, and then the biodiesel is prepared by transesterification with an alkali catalyst. If the effect of reducing the acid value of the pre-esterification is not up to the standard, the yield of the biodiesel in the subsequent reaction can be directly influenced, so that the higher the pre-esterification conversion rate in the process of preparing the biodiesel from the waste oil with the high acid value is, the lower the acid value is, and the higher the yield of the biodiesel is. Most of the pre-esterification catalysts used in the market are liquid acid catalysts, such as concentrated sulfuric acid, p-toluenesulfonic acid and the like, and have relatively high catalytic activity at a lower temperature, the pre-esterification conversion rate is high, but equipment is seriously corroded, and after the reaction is finished, a large amount of caustic soda needs to be added into reaction liquid for neutralization, so that a large amount of waste liquid and waste residues are generated, and meanwhile, the defects that the catalysts and raw material products are not easy to separate, continuous production is difficult to realize in the process and the like exist.
CN104004596A discloses that the problem of corrosion to equipment is solved by adopting ferric sulfate as a pre-esterification catalyst, but the subsequent processes of standing, extracting, stirring, filtering, drying and the like are needed for separating the catalyst from the product, and the operation process is complex. CN101016474A discloses a method for pretreating high acid value oil with solid acid, the yield of biodiesel after transesterification of soybean oil and oleic acid blended oil after solid acid treatment and methanol is more than 90%, but the yield of biodiesel for treating waste oil (acid value is 20.1) is only 84%, and the pre-esterification effect of the catalyst in waste oil containing more impurities is not ideal.
The invention aims to provide a solid acid catalyst for pre-esterification of high-acid-value waste oil and a preparation method and a using method thereof, wherein the solid acid catalyst has mild reaction conditions, is easy to separate and recycle with a product, can be recycled after activation, can treat the waste oil with the acid value of 140-260mg/g, and can be reused for 10 times, and the acid value can be reduced to 0.5-5; the catalyst can still maintain higher catalytic activity after continuous pre-esterification for 120 hours. The invention also provides two using methods of the solid acid catalyst for pre-esterification of the waste oil with high acid value, one method is used for intermittent stirring type production; the other is used in tower type continuous production.
Disclosure of Invention
In order to solve the technical problems, the application provides a solid acid catalyst for pre-esterification of high-acid-value waste oil and a preparation method and a using method thereof.
The solid acid catalyst comprises an alumina carrier, and a metal component and a nonmetal component which are loaded on the alumina carrier, wherein the chemical formula of the solid acid catalyst is M-Mo-P/Al2O3。
Preferably, M in the solid acid catalyst composition is one or more of Co, Ni, Sn and Sb.
A preparation method of a solid acid catalyst for pre-esterification of high-acid-value waste oil comprises the following steps:
(a) dissolving molybdate and diammonium hydrogen phosphate in water to prepare solution for later use;
(b) uniformly dropwise adding the solution prepared in the step (a) to gamma-Al2O3Uniformly stirring for 0.5-2 h, drying the obtained solid at 90-130 ℃ for 4-12h, and calcining at 400-800 ℃ for 1-6h to obtain Mo-P/Al2O3；
(c) Dissolving M salt in water to prepare M salt solution for later use;
(d) dropwise adding the M salt solution prepared in the step (c) into the Mo-P/Al solution prepared in the step (b)2O3Then the mixture is dried for 4 to 12 hours at the temperature of between 80 and 120 ℃ and calcined for 1 to 6 hours at the temperature of between 500 and 900 ℃ after being uniformly mixed to obtain the pre-esterification solid acid catalyst M-Mo-P/Al2O3。
Preferably, the mol ratio of the molybdate, the diammonium phosphate, the alumina, the M salt and the water is 0.01-0.1: 0.01-0.1:0.05-0.2: 0.01-0.1: 1.1-11; the molar ratio of molybdate to water in the step (a) is 0.01-0.1: 1-10; the molar ratio of M salt to water in the step (c) is 0.01-0.1: 0.1-1.
Preferably, the molybdate in step (a) is one or more of ammonium heptamolybdate, potassium molybdate and sodium molybdate.
Preferably, the diammonium phosphate described in step (a) may be replaced by sodium dihydrogen phosphate or disodium hydrogen phosphate or ammonium dihydrogen phosphate or phosphoric acid.
Preferably, the M salt in step (c) is one or more of cobalt sulfate, nickel sulfate, stannous chloride, antimony acetate and cobalt nitrate.
Preferably, the drying temperature in the step (b) is 110-; the drying temperature in the step (d) is 110 ℃, the drying time is 8-10h, the calcining temperature is 500-700 ℃, and the calcining time is 4-5 h.
A use method of a solid acid catalyst for pre-esterification of high acid value waste oil comprises the following two use methods:
(a) intermittent stirring production: adding the high-acid-value waste grease, methanol and a pre-esterification solid acid catalyst into a reactor according to the weight ratio of 0.4-1.8:1: 0.02-0.4, starting a reaction device, heating to 70-150 ℃, reacting for 1-12h, cooling to room temperature after the reaction is finished, filtering the catalyst, activating and recycling, distilling the filtrate under reduced pressure to evaporate unreacted methanol, measuring the acid value of a product, and calculating the pre-esterification rate;
(b) tower type continuous production: filling 0.02-0.4 part by weight of solid acid catalyst in a reactor, respectively introducing 0.4-1.8 parts by weight of high-acid-value waste oil and 1 part by weight of methanol into the reactor through a metering pump, reacting for 1-120h at 70-150 ℃, taking a product after the reaction is finished, measuring the acid value, and calculating the pre-esterification rate
Preferably, the initial acid value of the waste oil is 140-260 mgKOH/g.
The invention adopts SN/T0803.8-1999 import and export oil free fatty acid, acid value inspection method to measure the acid value before and after reaction, and calculates the pre-esterification rate.
The high-acid-value waste oil pre-esterification solid acid catalyst has good catalytic performance on pre-esterification of high-acid-value waste oil (140-260 mg KOH/g), and the acid value after pre-esterification can reach 0.5-5 mg KOH/g; the catalyst has no corrosion to reaction equipment, is easy to separate from reaction products, and is an environment-friendly solid acid catalyst; the catalyst can be repeatedly used after being activated, and the catalytic activity is not obviously reduced after 10 times of repeated use. The continuous reaction lasts for 120 hours, the catalytic activity is good, and the method has good industrial application prospect for treating the waste oil with high acid value.
Drawings
FIG. 1 is a process flow diagram of a batch reactor reaction of a high acid value waste oil pre-esterification solid acid catalyst according to the present invention;
FIG. 2 is a schematic diagram of a tower-type continuous reaction apparatus for pre-esterification of a high-acid-value waste oil and fat with a solid acid catalyst according to the present invention;
FIG. 3 is a diagram showing the result of the evaluation of the reuse of the high-acid-value waste oil pre-esterification solid acid catalyst according to the present invention;
FIG. 4 is a graph showing the evaluation results of the continuous esterification reaction of the high acid value waste oil pre-esterification solid acid catalyst of the present invention;
in the figure, 1, a reactor; 2. a preheater; 3. a nitrogen gas cylinder; 4. a methanol tank; 5. an injection pump; 6. a storage tank; 7. a water storage tank.
Detailed Description
Example 1
2.49g of ammonium molybdate, 2.66g of diammonium hydrogen phosphate and 38.20g of water are prepared into a solution, and the solution is uniformly dripped into 15.88g of alumina (gamma-Al) after standing2O3) Stirring for 1h, drying at 100 ℃ for 8h, and calcining at 500 ℃ for 1h to obtain Mo-P/Al2O3. 2.63g of nickel sulfate hexahydrate, 0.29g of antimony acetate and 7.91g of water are prepared into a solution which is dropwise added into Mo-P/Al2O3Drying at 80 ℃ for 12h, and calcining at 500 ℃ for 6h to obtain the pre-esterified solid acid catalyst Ni-Sb-Mo-P/Al2O3-1。
Respectively adding high acid value waste oil, methanol and a pre-esterification solid acid catalyst into a reactor, measuring the initial acid value, and reacting at 80 ℃, wherein the mass ratio of the methanol to the oil is 1.5: 1, adding 30% of catalyst by mass of grease, reacting for 12h, cooling to room temperature, filtering to separate out the catalyst, distilling the filtrate under reduced pressure to remove methanol, measuring acid value, and calculating pre-esterification rate. The process flow diagram is shown in FIG. 1, and the results are shown in Table 1.
Example 2
3.53g of ammonium molybdate, 1.66g of diammonium hydrogen phosphate and 20.42g of water are prepared into a solution, and the solution is stood still and uniformly dripped into 10.25g of alumina (gamma-Al)2O3) Stirring for 0.5 h, drying at 110 ℃ for 8h, and calcining at 500 ℃ for 2h to obtain Mo-P/Al2O3. 5.63g of cobalt sulfate, 0.45g of stannous chloride and 5.23g of water are prepared into a solution and dripped into Mo-P/Al2O3Drying at 110 ℃ for 10h, and calcining at 500 ℃ for 5h to obtain the pre-esterified solid acid catalyst Co-Sb-Mo-P/Al2O3-1。
Respectively adding high acid value waste oil, methanol and a pre-esterification solid acid catalyst into a reactor, measuring the initial acid value, and reacting at 100 ℃, wherein the mass ratio of the methanol to the oil is 1.5: 1, the adding mass of the catalyst is 20 percent of that of the grease. After 12h of reaction, cooling to room temperature, filtering to separate out the catalyst, distilling the filtrate under reduced pressure to remove methanol, collecting the fraction at 200-290 ℃, measuring the acid value, and calculating the pre-esterification rate. The process flow diagram is shown in FIG. 1, and the results are shown in Table 1.
Example 3
2.49g of ammonium molybdate, 1.96g of phosphoric acid and 38.20g of water are prepared into a solution, and the solution is evenly dripped into 15.88g of alumina (gamma-Al) after standing2O3) Stirring for 1h, drying at 120 ℃ for 10h, and calcining at 700 ℃ for 4h to obtain Mo-P/Al2O3. 5.82g of nickel nitrate hexahydrate, 0.29g of antimony acetate and 7.91g of water are prepared into a solution which is dripped into Mo-P/Al2O3Drying at 100 ℃ for 8h, and calcining at 700 ℃ for 4h to obtain the pre-esterified solid acid catalyst Ni-Sb-Mo-P/Al2O3-2。
The catalyst was used in the same manner as in example 1, and the results are shown in Table 1.
Example 4
3.53g of ammonium molybdate, 1.25g of phosphoric acid and 20.42g of water are prepared into a solution, and after standing, the solution is uniformly dripped into 10.25g of alumina (gamma-Al)2O3) Stirring for 0.5 h, drying at 100 deg.C for 8h, calcining at 400 deg.C for 2h, obtaining Mo-P/Al2O3. 5.91g of cobalt nitrate, 0.45g of stannous chloride and 5.23g of water are prepared into solution which is dripped into Mo-P/Al2O3Drying at 100 ℃ for 10h, and calcining at 800 ℃ for 3h to obtain the pre-esterified solid acid catalyst Co-Sb-Mo-P/Al2O3-2。
The catalyst was used in the same manner as in example 2, and the results are shown in Table 1.
Example 5
2.49g of ammonium molybdate, 2.66g of diammonium hydrogen phosphate and 38.20g of water are prepared into a solution, and the solution is uniformly dripped into 15.88g of alumina (gamma-Al) after standing2O3) Stirring for 1h, drying at 130 ℃ for 8h, and calcining at 800 ℃ for 1h to obtain Mo-P/Al2O3. 2.63g of nickel sulfate hexahydrate and 7.91g of water are prepared into a solution, the solution is dropwise added into Mo-P/Al2O3, drying is carried out at 80 ℃ for 12h, and calcination is carried out at 500 ℃ for 6h, so as to obtain the pre-esterification solid acid catalyst Ni-Mo-P/Al 2O 3.
The catalyst was used in the same manner as in example 1, and the results are shown in Table 1.
Example 6
3.53g of ammonium molybdate, 1.66g of diammonium hydrogen phosphate and 20.42g of water are prepared into a solution, the solution is uniformly dripped on 10.25g of alumina (gamma-Al 2O 3) after standing, the mixture is stirred for 2 hours, dried for 12 hours at 90 ℃, and calcined for 6 hours at 500 ℃ to obtain Mo-P/Al2O 3. 5.63g of cobalt sulfate and 5.23g of water are prepared into a solution, the solution is dripped on Mo-P/Al2O3, the solution is dried for 4 hours at 100 ℃, and calcined for 3 hours at 900 ℃ to obtain the pre-esterified solid acid catalyst Co-Mo-P/Al2O3。
The catalyst was used in the same manner as in example 2, and the results are shown in Table 1
Example 7
3.53g of ammonium molybdate, 1.66g of diammonium hydrogen phosphate and 20.42g of water are prepared into a solution, the solution is uniformly dripped on 10.25g of alumina (gamma-Al 2O 3) after standing, the mixture is stirred for 2 hours, dried for 12 hours at 90 ℃, and calcined for 6 hours at 500 ℃ to obtain Mo-P/Al2O 3. 1.20g of cobalt sulfate, 1.33g of nickel sulfate hexahydrate, 0.12g of antimony acetate, 1.55g of cobalt nitrate, 0.24g of stannous chloride and 5.23g of water are prepared into a solution, the solution is dripped on Mo-P/Al2O3, the drying is carried out for 4h at 100 ℃, the calcination is carried out for 3h at 900 ℃, and the pre-esterification solid acid catalyst Co-Mo-P/Al is obtained2O3。
The catalyst was used in the same manner as in example 1, and the results are shown in Table 1.
Example 8
The catalyst was prepared in the same manner as in example 1.
Respectively adding high acid value waste oil, methanol and a pre-esterification solid acid catalyst into a reactor, measuring the initial acid value, and reacting at 90 ℃, wherein the mass ratio of the methanol to the oil is 1.5: 1, the adding mass of the catalyst is 20 percent of that of the grease. After 12h of reaction, cooling to room temperature, filtering to separate out the catalyst, activating for later use, distilling the filtrate under reduced pressure, collecting the fraction at 200-290 ℃, measuring the acid value, and calculating the pre-esterification rate. The separated catalyst is washed by absolute methanol and filtered, and the reaction is repeatedly carried out after drying. The total number of repeated use is 10 times, the acid value is recorded after each reaction, and the pre-esterification rate is calculated. The process flow diagram is shown in FIG. 1, and the results are shown in Table 2 and FIG. 3.
Example 9
The catalyst was prepared in the same manner as in example 1.
1.5g of solid acid catalyst is filled in a reactor, the temperature of the reactor is set to be 150 ℃, waste grease with high acid value is pumped into the reactor at the speed of 5m L/h, 50m L/h of methanol enters the reactor through a preheater (120 ℃), and the mass space velocity is 1.5 h-1And reacting for 120h, taking the product every 12h to measure the acid value, calculating the pre-esterification rate, and showing the reaction device schematic diagram in figure 2 and the result in table 3 and figure 4.
As can be seen from the figures and tables, the catalyst described in the application treats the waste oil with acid value of 140-260, and is reused for 10 times, and the catalytic effect of the catalyst is basically unchanged; the catalyst can still maintain higher catalytic activity after continuous pre-esterification for 120 hours.
The method measures the acid value before and after the reaction by using SN/T0803.8-1999 import and export oil free fatty acid and acid value inspection method, and calculates the pre-esterification rate.
The technical scheme of the invention is not limited to all the following specific embodiments, and also comprises any combination of the specific embodiments; the high activity prepared by taking alumina as a carrier and loading metal elements can be used for the pre-esterification reaction of the high-acid-value waste oil, the pre-esterification rate is more than 95%, and the catalytic activity is higher; the catalyst has no corrosion to equipment, is green and environment-friendly, and is a green and environment-friendly solid acid catalyst.
Claims (16)
1. The application of the solid acid catalyst in the pre-esterification of the high-acid-value waste oil is characterized in that the solid acid catalyst comprises an alumina carrier, and a metal component and a nonmetal component which are loaded on the alumina carrier, wherein the chemical formula of the solid acid catalyst is M-Mo-P/Al2O3(ii) a In the composition of the solid acid catalyst, M is one or more of Co, Ni, Sn and Sb; the using method comprises the following steps:
(a) intermittent stirring production: adding the high-acid-value waste grease, methanol and a pre-esterification solid acid catalyst into a reactor according to the weight ratio of 0.4-1.8:1: 0.02-0.4, starting a reaction device, heating to 70-150 ℃, reacting for 1-12h, cooling to room temperature after the reaction is finished, filtering the catalyst, activating and recycling, distilling the filtrate under reduced pressure to evaporate unreacted methanol, measuring the acid value of the product, and calculating the pre-esterification rate.
2. The use of the solid acid catalyst in the pre-esterification of high acid value waste oil and fat according to claim 1, wherein the initial acid value of the waste oil and fat is 140-260mgKOH/g of industrial waste oil and fat.
3. Use according to claim 1 or 2, characterized in that the process for the preparation of the solid acid catalyst comprises the following steps:
(a) dissolving molybdate and diammonium hydrogen phosphate in water to prepare solution for later use;
(b) uniformly dropwise adding the solution prepared in the step (a) to gamma-Al2O3Uniformly stirring for 0.5-2 h, drying the obtained solid at 90-130 ℃ for 4-12h, and calcining at 400-800 ℃ for 1-6h to obtain Mo-P/Al2O3；
(c) Dissolving M salt in water to prepare M salt solution for later use;
(d) dropwise adding the M salt solution prepared in the step (c) into the Mo-P/Al solution prepared in the step (b)2O3Then the mixture is dried for 4 to 12 hours at the temperature of between 80 and 120 ℃ and calcined for 1 to 6 hours at the temperature of between 500 and 900 ℃ after being uniformly mixed to obtain the pre-esterification solid acid catalyst M-Mo-P/Al2O3。
4. The use according to claim 3, wherein the molar ratio of molybdate, diammonium phosphate, alumina, M salt, water is 0.01-0.1: 0.01-0.1:0.05-0.2: 0.01-0.1: 1.1-11; the molar ratio of molybdate to water in the step (a) is 0.01-0.1: 1-10; the molar ratio of M salt to water in the step (c) is 0.01-0.1: 0.1-1.
5. The use according to claim 3, wherein the molybdate in step a is one or more of ammonium heptamolybdate, potassium molybdate and sodium molybdate.
6. Use according to claim 3, wherein the diammonium phosphate in step (a) is replaced by sodium or disodium hydrogen phosphate or ammonium dihydrogen phosphate or phosphoric acid.
7. The use according to claim 3, wherein the M salt in step (c) is one or more of cobalt sulfate, nickel sulfate, stannous chloride, antimony acetate and cobalt nitrate.
8. The method as claimed in claim 3, wherein the drying temperature in step (b) is 110-120 ℃, the drying time is 8-10h, the calcination temperature is 500-700 ℃, and the calcination time is 2-4 h; the drying temperature in the step (d) is 110 ℃, the drying time is 8-10h, the calcining temperature is 500-700 ℃, and the calcining time is 4-5 h.
9. The application of the solid acid catalyst in the pre-esterification of the high-acid-value waste oil is characterized in that the solid acid catalyst comprises an alumina carrier, and a metal component and a nonmetal component which are loaded on the alumina carrier, wherein the chemical formula of the solid acid catalyst is M-Mo-P/Al2O3(ii) a In the composition of the solid acid catalyst, M is one or more of Co, Ni, Sn and Sb; the using method comprises the following steps:
(b) tower type continuous production: filling 0.02-0.4 part by weight of solid acid catalyst into a reactor, respectively introducing 0.4-1.8 parts by weight of high-acid-value waste oil and 1 part by weight of methanol into the reactor through a metering pump, reacting for 1-120h at the temperature of 70-150 ℃, taking a product after the reaction is finished, measuring the acid value, and calculating the pre-esterification rate.
10. The use of the solid acid catalyst in the pre-esterification of high acid value waste oil and fat according to claim 9, wherein the initial acid value of the waste oil and fat is 140-260mgKOH/g of industrial waste oil and fat.
11. Use according to claim 9 or 10, characterized in that the process for the preparation of the solid acid catalyst comprises the following steps:
(a) dissolving molybdate and diammonium hydrogen phosphate in water to prepare solution for later use;
(b) uniformly dropwise adding the solution prepared in the step (a) to gamma-Al2O3Uniformly stirring for 0.5-2 h, drying the obtained solid at 90-130 ℃ for 4-12h, and calcining at 400-800 ℃ for 1-6h to obtain Mo-P/Al2O3；
(c) Dissolving M salt in water to prepare M salt solution for later use;
(d) dropwise adding the M salt solution prepared in the step (c) into the Mo-P/Al solution prepared in the step (b)2O3Mixing uniformly at 8Drying at 0-120 ℃ for 4-12h, calcining at 500-900 ℃ for 1-6h to obtain the pre-esterified solid acid catalyst M-Mo-P/Al2O3。
12. The use according to claim 11, wherein the molar ratio of molybdate, diammonium phosphate, alumina, M-salt, water is 0.01-0.1: 0.01-0.1:0.05-0.2: 0.01-0.1: 1.1-11; the molar ratio of molybdate to water in the step (a) is 0.01-0.1: 1-10; the molar ratio of M salt to water in the step (c) is 0.01-0.1: 0.1-1.
13. The use according to claim 11, wherein the molybdate in step a is one or more of ammonium heptamolybdate, potassium molybdate and sodium molybdate.
14. Use according to claim 11, wherein the diammonium phosphate in step (a) is replaced by sodium or disodium hydrogen phosphate or ammonium dihydrogen phosphate or phosphoric acid.
15. The use according to claim 11, wherein the M salt in step (c) is one or more of cobalt sulfate, nickel sulfate, stannous chloride, antimony acetate and cobalt nitrate.
16. The method as claimed in claim 11, wherein the drying temperature in step (b) is 110-120 ℃, the drying time is 8-10h, the calcination temperature is 500-700 ℃, and the calcination time is 2-4 h; the drying temperature in the step (d) is 110 ℃, the drying time is 8-10h, the calcining temperature is 500-700 ℃, and the calcining time is 4-5 h.
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