CN115725363A - Process for preparing second-generation biodiesel by hydrogenating waste oil - Google Patents
Process for preparing second-generation biodiesel by hydrogenating waste oil Download PDFInfo
- Publication number
- CN115725363A CN115725363A CN202211376662.XA CN202211376662A CN115725363A CN 115725363 A CN115725363 A CN 115725363A CN 202211376662 A CN202211376662 A CN 202211376662A CN 115725363 A CN115725363 A CN 115725363A
- Authority
- CN
- China
- Prior art keywords
- oil
- catalyst
- waste
- hydrogenation
- hydrofining
- 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.)
- Pending
Links
- 239000003225 biodiesel Substances 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
- 239000004519 grease Substances 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 101
- 235000019198 oils Nutrition 0.000 claims description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 235000019482 Palm oil Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002540 palm oil Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000010775 animal oil Substances 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000021190 leftovers Nutrition 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 32
- 239000002253 acid Substances 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 235000021314 Palmitic acid Nutrition 0.000 description 7
- 239000003925 fat Substances 0.000 description 7
- 235000019197 fats Nutrition 0.000 description 7
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- 239000010724 circulating oil Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 235000019737 Animal fat Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241001048891 Jatropha curcas Species 0.000 description 1
- 240000002924 Platycladus orientalis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
Classifications
-
- 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
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the technical field of biodiesel preparation, and particularly relates to a process for preparing second-generation biodiesel by hydrogenating waste oil, wherein the process is used for preparing the second-generation biodiesel by sequentially carrying out pre-hydrogenation treatment and hydrofining treatment on the waste oil;wherein the catalyst A adopted in the step of pre-hydrogenation treatment takes a carbon-based material as a carrier, and the specific surface area of the carrier is 300-850 m 2 The pore volume is 0.19-0.53 mL/g. The catalyst A not only can effectively protect the subsequent hydrofining catalyst from being poisoned, thereby avoiding the problems that the process can not run stably for a long period and has high cost due to frequent replacement of the hydrofining catalyst, but also expands the range of raw materials for producing biodiesel, so that the process of the invention not only can be used for treating high-quality biological grease, but also can be suitable for treating low-quality grease with high acid value. The process has mild reaction conditions, does not produce waste water, waste acid and solid waste, and greatly reduces the environmental protection pressure.
Description
Technical Field
The invention belongs to the technical field of biodiesel preparation, and particularly relates to a process for preparing second-generation biodiesel by hydrogenating waste oil.
Background
The continuous decrease of petroleum resources and the fluctuation of petroleum prices have made the energy supply diversified, and the development of renewable clean alternative energy sources is necessary. The biological oil is a renewable energy source, and the preparation of biodiesel and other chemical raw materials by taking the biological oil as a raw material is an important development direction of alternative energy sources. The biological oil and fat resources comprise vegetable oil (such as soybean oil, rapeseed oil, palm oil, jatropha curcas oil, chinese arborvitae oil, etc.), animal fat (such as lard, beef tallow, fish oil, etc.), waste oil, acidified oil, restaurant waste oil, etc.
The biodiesel is a substitute of petroleum-based diesel oil prepared from animal and vegetable oil as raw materials, and the first generation biodiesel mainly comprises fatty acid low-carbon alcohol ester, particularly methyl ester. Compared with common diesel oil from petroleum, the fatty acid methyl ester has the advantages of low sulfur content, less pollution, use of renewable raw materials and the like. However, the performance of the first generation biodiesel is not good enough due to the influence of the saturation degree of the carbon chains in the used raw materials, and if the saturation degree of the carbon chains in the raw materials is high, the biodiesel is easy to separate out and block a conveying pipeline when used in a cold season; if the saturation is low, the unsaturated bond content is high, so that the unsaturated bond is easy to oxidize and deteriorate, is difficult to store and affects the use performance.
The second generation biodiesel is fuel obtained by hydrodeoxygenation and hydroisomerization of animal and vegetable oil. The second generation biodiesel is closer to petroleum-based fuels in structure and performance, and therefore is superior to the first generation biodiesel in both processing and use. The biodiesel is prepared from animal and vegetable oil, such as animal fat (beef tallow, mutton fat, fish fat of fish processing waste), soybean oil (America), rapeseed oil (Europe), palm oil (southeast Asia) and the like, while the raw materials used by domestic enterprises are mainly waste oil such as waste meal oil and palmitic acid oil, the raw materials are relatively miscellaneous in source, unstable in property, high in metal content, high in acid value and insoluble impurities, easy to condense and deteriorate and the like, and can be subjected to hydrogenation treatment after being pretreated. At present, the raw materials are generally pretreated by acid washing, water washing and argil adsorption and other processes in industry, and the problems of long process flow, more generated wastewater, waste acid and solid waste, higher environmental protection pressure and loss in the treatment process exist. The method can affect the activity of the hydrogenation catalyst if the hydrogenation catalyst is directly subjected to hydrogenation catalysis without pretreatment, frequent shutdown and replacement of the catalyst are required, so that continuous production cannot be realized, the cost of the whole process is overhigh due to the high price of the catalyst, and the purity of the second-generation finished biodiesel prepared by the method is low, so that the requirement of industrial application cannot be met.
Therefore, the prior art discloses a method for producing biodiesel by using biological oil, which comprises the steps of enabling raw oil and hydrogen to pass through a hydrogenation reactor operated at a low temperature, then passing through a hydrogenation reactor operated at a high temperature, and filling hydrogenation catalysts in two-stage hydrogenation reactors, thereby preparing a high-quality diesel product. The technology adopts high-quality biological oil such as soybean oil, rapeseed oil, cottonseed oil and the like which mainly comprise esters as raw materials, which inevitably increases the production cost of the product; and the hydrogenation catalysts adopted by the two-stage hydrogenation all use alumina as a carrier, and molybdenum and nickel or cobalt as metal active components, and the hydrogenation catalysts are expensive, more importantly, the hydrogenation catalysts are easily poisoned by metals, oxygen and the like in raw materials, the catalysts need to be frequently replaced, and the long-period stable operation of the process cannot be ensured, so that the prior art cannot be used for treating the raw materials with poor quality at all.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the existing process for producing biodiesel by using biological oil and fat to carry out two-stage hydrogenation cannot be stably operated for a long period, cannot be used for processing biological oil and fat with low quality and high acid value and has high production cost, and further provide a production process of second-generation biodiesel.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing second-generation biodiesel by hydrogenating waste oil comprises the following steps:
sequentially carrying out pre-hydrogenation treatment and hydrofining treatment on the waste oil to obtain the waste oil;
the catalyst A adopted in the pre-hydrogenation treatment step is a carbon-based material as a carrier, and the specific surface area of the carrier is 300-850 m 2 The pore volume is 0.19-0.53 mL/g.
Preferably, the carbon-based material is wood activated carbon and/or coal activated carbon.
Preferably, the active component of the catalyst A is at least one of nickel, molybdenum and cobalt in an oxidation state.
Preferably, the content of the active component in the catalyst A is 3wt% to 20wt%.
Preferably, the process conditions of the pre-hydrotreatment include: the liquid space velocity is 0.5 to 2 hours -1 The volume ratio of hydrogen to oil is 500-2000, the reaction pressure is 2-8 MPa, and the reaction temperature is 160-280 ℃.
Preferably, the hydrorefining step adopts a catalyst B, and the active components of the catalyst B are at least two of nickel, molybdenum, cobalt and tungsten in oxidation states.
Preferably, the content of the active component in the catalyst B is 20wt% to 40wt%.
Preferably, the carrier of the catalyst B is an alumina carrier.
Preferably, the process conditions of the hydrofining treatment include: the liquid space velocity is 0.5 to 2 hours -1 The volume ratio of hydrogen to oil is 500:1 to 2000:1, the reaction temperature is 280-340 ℃, and the reaction pressure is 8-12 MPa.
Preferably, at least two pre-hydrogenation reaction devices connected in parallel are adopted in the pre-hydrogenation treatment step, and the outlet of any one pre-hydrogenation reaction device is connected with the inlet of the hydrofining device adopted in the hydrofining treatment step.
Preferably, the waste oil includes, but is not limited to, at least one of acidified oil, industrial palm oil, waste water from palm oil production, hogwash oil, animal oil and fat, and leftover of oil and fat processing plant.
Preferably, the process further comprises a separation step after the hydrofining step, wherein the separation step comprises the steps of carrying out oil-water separation on the hydrofined material, collecting an oil phase, and then carrying out fractionation treatment on the oil phase to obtain the second-generation biodiesel.
Optionally, the process further comprises mixing part of the secondary diesel oil or part of the secondary diesel oil with tail oil in the fractionation step to be used as circulating oil, and recycling the circulating oil to the hydrogenation pretreatment step to be mixed with the waste grease.
The method comprises the steps of using waste oil as a raw material, carrying out pre-hydrogenation treatment under the action of a catalyst A, carrying out partial deoxidation, demetalization, olefin saturation and other reactions, carrying out hydrofining treatment on the obtained material to obtain a crude bio-alkane, carrying out oil-water separation on the obtained crude bio-alkane to obtain a product oil, and carrying out fractionation on the product oil to remove light hydrocarbon components to obtain high-purity long-chain straight-chain alkane of C13-C22, namely the finished product of the second-generation biodiesel.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the process for preparing the second-generation biodiesel by hydrogenating the waste oil comprises the steps of carrying out pre-hydrogenation treatment and hydrofining treatment on the waste oil in sequence, wherein a catalyst A adopted in the pre-hydrogenation treatment step is a carbon-based material as a carrier, and the specific surface area of the carrier is 300-850 m 2 The pore volume is 0.19-0.53 mL/g. The catalyst A has developed pore structure, large specific surface area, strong adsorption capacity, stable chemical property, acid resistance, water resistance and high temperature resistance, and can be subjected to a pre-hydrogenation treatment stepMetal and phospholipid in the low-quality raw material are removed, olefin is saturated, partial deoxidation is carried out, on one hand, the subsequent hydrofining catalyst can be effectively protected from being poisoned, so that the problems that the process cannot be stably operated for a long period and is high in cost due to frequent replacement of the hydrogenation catalyst are avoided, on the other hand, the raw material range for producing the biodiesel is enlarged, so that the process not only can be used for treating high-quality biological oil, but also can be suitable for processing low-quality and high-acid-value oil, such as waste oil of acid oil, industrial palm oil, palm oil production wastewater, oil processing plant leftovers and the like, and the process cost is further reduced.
2. The process for preparing the second-generation biodiesel by hydrogenating the waste oil provided by the embodiment of the invention preferably has the liquid airspeed of 0.5-2 h -1 The method comprises the following steps of (1) performing pre-hydrogenation treatment on a raw material under the conditions that the volume ratio of hydrogen to oil is 500-2000, the reaction pressure is 2-8 MPa, and the reaction temperature is 160-280 ℃, and the inventor finds that the pre-hydrogenation treatment conditions can enable the catalyst A to exert the catalytic effect to the maximum extent, and the catalyst A and the pre-hydrogenation treatment can reduce the iodine value of the raw material by over 81 percent, reduce the acid value by at least 82 percent, achieve the metal removal rate of 86 percent, and achieve the oxygen removal rate of about 65 percent under the combined action, so that the subsequent hydrorefining catalyst is effectively protected.
In addition, the reaction conditions of the process are mild, no waste water, waste acid or solid waste is generated, and the environmental protection pressure is greatly reduced.
3. According to the process for preparing the second-generation biodiesel by hydrogenating the waste oil, at least two pre-hydrogenation reaction devices connected in parallel are adopted in the pre-hydrogenation treatment step, and the outlet of any one pre-hydrogenation reaction device is connected with the inlet of a hydrofining device adopted in the hydrofining treatment step. The pre-hydrogenation section adopts at least two reactors which are arranged in parallel and can be switched for use, so that the catalyst can be maintained or replaced without stopping the reaction, the production process is not influenced, the production efficiency is improved, and the long-period stable operation of the process is further ensured.
4. According to the process for preparing the second-generation biodiesel by hydrogenating the waste oil, provided by the embodiment of the invention, part of product oil or a mixture of part of product oil and tail oil in the fractionation step is used as circulating oil and recycled to the hydrogenation pretreatment step to be mixed with the raw material oil, so that the acid value and the impurity content of the raw material oil can be reduced, the over-high temperature of a reactor can be prevented, and the smooth operation of the hydrogenation step is facilitated.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The composition and properties of the catalysts used in the examples of the present invention are shown in Table 1, respectively.
TABLE 1 composition and Properties of the catalysts
In the embodiments of the present invention, an in-situ presulfurization mode is adopted to convert the active metal component of the catalyst from an oxidation state to a sulfidation state, and a sulfur-containing medium such as dimethyl disulfide (DMDS), CS is supplemented in the reaction system at the right moment 2 And the content of hydrogen sulfide in the recycle gas is not less than 0.015v%, preferably 0.01 to 2v%. This is a common practice in the prior art and will not be described in detail in the following embodiments.
The grease performance detection is carried out by adopting the following method in the embodiment of the invention:
iodine value: according to a GB/T5532-2008 method for measuring iodine values of animal and vegetable fats and oils.
Acid value: according to the method for measuring the acid value of the food in GB 5009.229-2016 food safety national standard.
Metal removal rate: the metal content before and after the hydrogenation of the waste grease is measured according to the method for measuring additive elements, wear metals and pollutants in the used lubricating oil and certain elements in the base oil (inductively coupled plasma emission spectrometry) in GB/T17476-1998, and the metal content is obtained by calculation.
Oxygen removal rate: and (3) measuring the oxygen content in the oil product before and after hydrogenation by using an automatic element analyzer, and calculating to obtain the product.
Example 1
The process for preparing the second-generation biodiesel by hydrogenating the waste oil comprises the following steps:
heating the palmitic acid oil, and mixing the palmitic acid oil with cycle oil (namely a mixture formed by mixing the product oil and tail oil prepared in the embodiment in a mass ratio of 3:1, the mixed raw material is pressurized by a pressurizing feed pump, and then mixed with hydrogen to enter a fixed bed reactor for a pre-hydrogenation reaction, the fixed bed reactor is filled with a catalyst A1 (the composition and properties of the catalyst are shown in Table 1), and the pre-hydrogenation reaction conditions are as follows: the liquid space velocity is 0.5h -1 The hydrogen-oil ratio is 700:1, the reaction pressure is 8MPa, and the reaction temperature is 280 ℃.
Feeding the material from the fixed bed reactor into a hydrorefining reactor for hydrorefining treatment, wherein the hydrorefining reactor is filled with a catalyst B1 (the composition and properties of the catalyst B are shown in Table 1), and the hydrorefining reaction conditions are as follows: space velocity of 2h -1 The hydrogen-oil ratio is 700:1, the reaction pressure is 8MPa, and the reaction temperature is 320 ℃.
And (3) performing oil-water separation on the material flowing out of the hydrofining reactor according to the conventional operation to obtain gas, an oil phase and water. And finally, sending the oil phase obtained by oil-water separation into a fractionating tower, fractionating light hydrocarbon and second-generation biodiesel (namely product oil), and leaving tail oil at the bottom of the fractionating tower.
The second generation biodiesel prepared in this example was found to have a density of 0.7761g/mL, a cetane number of 86, and a yield of 86.3%. The properties of the mixed raw material of this example before and after the prehydrogenation are shown in Table 2.
TABLE 2 Change in Properties of the Mixed raw Material before and after prehydrogenation
Example 2
The process for preparing the second-generation biodiesel by hydrogenating the waste oil comprises the following steps of:
heating the palmitic acid oil, and mixing the heated palmitic acid oil with cycle oil (namely a mixture formed by mixing the product oil prepared in the embodiment and tail oil according to a mass ratio of 3:1, the mixed raw material is pressurized by a pressurizing feed pump and then mixed with hydrogen to enter a fixed bed reactor for pre-hydrogenation reaction, the fixed bed reactor is filled with a catalyst A2 (the composition and properties of the catalyst are shown in Table 1), and the conditions of the pre-hydrogenation reaction are as follows: the liquid space velocity is 1h -1 The hydrogen-oil ratio is 2000.
Feeding the material flowing out of the fixed bed reactor into a hydrofining reactor for hydrofining treatment, wherein the hydrofining reactor is filled with a catalyst B1 (the composition and properties of the catalyst B are shown in Table 1), and the hydrofining reaction conditions are as follows: the space velocity is 0.5h -1 The hydrogen-oil ratio is 1000.
And (3) performing oil-water separation on the material flowing out of the hydrofining reactor according to the conventional operation to obtain gas, an oil phase and water. And finally, sending the oil phase obtained by oil-water separation into a fractionating tower, fractionating light hydrocarbon and second-generation biodiesel (namely product oil), and leaving tail oil at the bottom of the fractionating tower.
The second generation biodiesel prepared in this example was found to have a density of 0.7883g/mL, a cetane number of 81, and a yield of 82.5%. The properties of the mixed raw material of this example before and after the prehydrogenation are shown in Table 3.
TABLE 3 Change in Properties of the Mixed raw Material before and after prehydrogenation
Example 3
The process for preparing the second-generation biodiesel by hydrogenating the waste oil comprises the following steps of:
heating the palmitic acid oil, and mixing the heated palmitic acid oil with cycle oil (namely a mixture formed by mixing the product oil prepared in the embodiment and tail oil according to a mass ratio of 1:1, the mixed raw material is pressurized by a pressurizing feed pump, and then mixed with hydrogen to enter a fixed bed reactor for a pre-hydrogenation reaction, the fixed bed reactor is filled with a catalyst A3 (the composition and properties of the catalyst are shown in Table 1), and the pre-hydrogenation reaction conditions are as follows: the liquid space velocity is 2h -1 The hydrogen-oil ratio is 1500.
Feeding the material from the fixed bed reactor into a hydrorefining reactor for hydrorefining treatment, wherein the hydrorefining reactor is filled with a catalyst B1 (the composition and properties of the catalyst B are shown in Table 1), and the hydrorefining reaction conditions are as follows: space velocity of 1h -1 The hydrogen-oil ratio is 1500.
And (3) performing oil-water separation on the material flowing out of the hydrofining reactor according to the conventional operation to obtain gas, an oil phase and water. And finally, sending the oil phase obtained by oil-water separation into a fractionating tower, fractionating light hydrocarbon and second-generation biodiesel (namely product oil), and leaving tail oil at the bottom of the fractionating tower.
The second generation biodiesel prepared in this example was found to have a density of 0.7802g/mL, a cetane number of 84, and a yield of 85.1%. The properties of the mixed raw material of this example before and after the prehydrogenation are shown in Table 4.
TABLE 4 Change in Properties of the Mixed raw materials before and after prehydrogenation
Comparative example 1
The contents are the same as those of example 3 except for the following.
Catalyst A4 was used in place of catalyst A3 in the prehydrogenation step.
The second-generation biodiesel prepared by the comparative example has the density of 0.7789g/mL, the cetane number of 84 and the yield of 84.2 percent through detection. The properties of the mixed starting material of this comparative example before and after the prehydrogenation are shown in Table 5.
TABLE 5 Change in Properties of the Mixed raw materials before and after prehydrogenation
Comparative example 2
The contents are the same as those of example 1 except for the following.
Catalyst A5 was used in place of catalyst A1 in the prehydrogenation step.
The second generation biodiesel prepared by the comparative example has the density of 0.7775g/mL, the cetane number of 83 and the yield of 84.6 percent through detection. The properties of the mixed raw material of this comparative example before and after the prehydrogenation treatment are shown in Table 6.
TABLE 6 Properties of the Mixed raw materials before and after prehydrogenation
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A process for preparing second-generation biodiesel by hydrogenating waste oil is characterized by comprising the following steps:
sequentially carrying out pre-hydrogenation treatment and hydrofining treatment on the waste oil to obtain the waste oil;
the catalyst A adopted in the pre-hydrogenation step takes a carbon-based material as a carrier, and the specific surface area of the carrier is 300-850 m 2 The pore volume is 0.19-0.53 mL/g.
2. The process of claim 1, wherein the carbon-based material is wood-based activated carbon and/or coal-based activated carbon.
3. The process of claim 1, wherein the active component of catalyst a is at least one of nickel, molybdenum, cobalt in an oxidized state; and/or
The content of the active component in the catalyst A is 3wt% -20wt%.
4. The process of any of claims 1 to 3, wherein the process conditions of the pre-hydrotreating comprise: the liquid space velocity is 0.5 to 2 hours -1 The volume ratio of hydrogen to oil is 500-2000.
5. The process according to claim 1, wherein the hydrofining treatment step adopts a catalyst B, and active components of the catalyst B are at least two of nickel, molybdenum, cobalt and tungsten in oxidation states; and/or
The content of the active component in the catalyst B is 20wt% -40 wt%.
6. The process of claim 5, wherein the support of catalyst B is an alumina support.
7. The process of claim 1, wherein the process conditions of the hydrofinishing treatment include: the liquid space velocity is 0.5 to 2 hours -1 The volume ratio of hydrogen to oil is 500:1 to 2000:1, the reaction temperature is 280-340 ℃, and the reaction pressure is 8-12 MPa.
8. The process according to claim 1, wherein at least two pre-hydrogenation reaction devices are used in the pre-hydrotreating step, and the outlet of any one of the pre-hydrogenation reaction devices is connected to the inlet of the hydrofining device used in the hydrofining step.
9. The process of claim 1, wherein the waste oil comprises at least one of but not limited to acidified oil, industrial palm oil, waste water from palm oil production, hogwash oil, animal oil, and leftovers from oil processing plants.
10. The process according to claim 1, 2, 3, 5, 6, 7, 8 or 9, further comprising a separation step after the hydrofinishing treatment step, wherein the separation step comprises performing oil-water separation on the hydrofinished material, collecting an oil phase, and performing fractionation on the oil phase to obtain the second-generation biodiesel;
optionally, the process further comprises mixing part of the second-generation diesel oil or part of the second-generation diesel oil with tail oil in the fractionation step to serve as cycle oil, and recycling the cycle oil to the hydrogenation pretreatment step to be mixed with the waste grease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211376662.XA CN115725363A (en) | 2022-11-04 | 2022-11-04 | Process for preparing second-generation biodiesel by hydrogenating waste oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211376662.XA CN115725363A (en) | 2022-11-04 | 2022-11-04 | Process for preparing second-generation biodiesel by hydrogenating waste oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115725363A true CN115725363A (en) | 2023-03-03 |
Family
ID=85294544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211376662.XA Pending CN115725363A (en) | 2022-11-04 | 2022-11-04 | Process for preparing second-generation biodiesel by hydrogenating waste oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115725363A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328830A (en) * | 2023-04-06 | 2023-06-27 | 北京海新能源科技股份有限公司 | Sulfurized hydroisomerization catalyst, and preparation method and application thereof |
| CN117801881A (en) * | 2024-02-26 | 2024-04-02 | 北京海新能源科技股份有限公司 | Pretreatment method for waste grease |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
| CN107573968A (en) * | 2017-09-18 | 2018-01-12 | 肖连朝 | A kind of method that high-purity biology alkane is prepared using waste grease |
| CN109294746A (en) * | 2017-07-25 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of method that grease type raw material adds hydrogen to prepare diesel oil distillate |
| CN110628512A (en) * | 2019-08-29 | 2019-12-31 | 易高生物化工科技(张家港)有限公司 | Hydrotreating method for chlorine-containing waste animal and vegetable oil |
| CN113578352A (en) * | 2021-09-01 | 2021-11-02 | 福州大学化肥催化剂国家工程研究中心 | High-stability fixed bed hydrodeoxygenation catalyst and preparation method and application thereof |
-
2022
- 2022-11-04 CN CN202211376662.XA patent/CN115725363A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
| CN109294746A (en) * | 2017-07-25 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of method that grease type raw material adds hydrogen to prepare diesel oil distillate |
| CN107573968A (en) * | 2017-09-18 | 2018-01-12 | 肖连朝 | A kind of method that high-purity biology alkane is prepared using waste grease |
| CN110628512A (en) * | 2019-08-29 | 2019-12-31 | 易高生物化工科技(张家港)有限公司 | Hydrotreating method for chlorine-containing waste animal and vegetable oil |
| CN113578352A (en) * | 2021-09-01 | 2021-11-02 | 福州大学化肥催化剂国家工程研究中心 | High-stability fixed bed hydrodeoxygenation catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 掌子龙;蒋惠亮;范明明;成取林;: "油脂加氢活性炭负载镍系催化剂的研究", 应用化工, no. 01, pages 86 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328830A (en) * | 2023-04-06 | 2023-06-27 | 北京海新能源科技股份有限公司 | Sulfurized hydroisomerization catalyst, and preparation method and application thereof |
| CN116328830B (en) * | 2023-04-06 | 2024-04-26 | 北京海新能源科技股份有限公司 | Sulfurized hydroisomerization catalyst, and preparation method and application thereof |
| CN117801881A (en) * | 2024-02-26 | 2024-04-02 | 北京海新能源科技股份有限公司 | Pretreatment method for waste grease |
| CN117801881B (en) * | 2024-02-26 | 2024-06-04 | 北京海新能源科技股份有限公司 | Pretreatment method for waste grease |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115725363A (en) | Process for preparing second-generation biodiesel by hydrogenating waste oil | |
| CN102746871B (en) | From the method for biological oil and fat preparation fuel | |
| BRPI0811661B1 (en) | HYDROTREATMENT PROCESS OF A LIQUID FOOD AND HYDRODEOXYGENATION PROCESSES OF A RENEWABLE RESOURCE | |
| CN108504381B (en) | Method for preparing diesel oil with high cetane number by directly hydrogenating animal and vegetable oil | |
| CN111978987B (en) | Method for producing aviation kerosene by combining aviation kerosene, biomass oil and coal tar | |
| CN112048340A (en) | Method for producing second-generation biodiesel and aviation fuel by three-step combined process | |
| CN104250558A (en) | Method for producing normal paraffin by hydrogenating fatty acid ester | |
| Popov et al. | Renewable fuels via catalytic hydrodeoxygenation of lipid-based feedstocks | |
| MX2014011755A (en) | Methods and apparatuses for processing renewable feedstocks. | |
| CN102492455A (en) | Method for preparing fuel from biological grease | |
| CN112592737A (en) | Method for producing low-freezing point biodiesel by coupling liquid catalysis with heterogeneous pour point depression | |
| CN102464996B (en) | Hydrogenation method for producing biological grease by motor fuel | |
| US20160289070A1 (en) | Processes for producing hydrogen gas stream from an offgas stream | |
| CN112592732A (en) | Method for producing second-generation biodiesel | |
| CN116790288B (en) | Method for producing biological aviation kerosene by hydrogenating waste grease | |
| CN116554926B (en) | Method for producing biodiesel by hydrogenating waste grease | |
| CN103102920B (en) | The two-stage method method of hydrotreating of production high-quality solvent oil | |
| CN103102918B (en) | Two-stage hydrogenation method for producing solvent oil | |
| CN103102901B (en) | Hydrogenation method for producing low aromatic hydrocarbon solvent oil from biological oil | |
| CN114763492B (en) | Biodiesel production method | |
| CN103102897A (en) | Hydrogenation method for production of low-condensation point motor fuel from biolipid | |
| CN103102912B (en) | Two-stage hydrogenation method for producing high quality low freezing point motor fuel | |
| CN116970420A (en) | Production process for processing biological oil | |
| CN116376595A (en) | Process method for producing renewable aviation fuel by medium-low pressure hydrogenation | |
| CN117304975A (en) | Method for preparing biodiesel by hydrodeoxygenation and quality improvement of biological grease |
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 |