CN105264046B - 使基于生物的材料脱氧的方法以及基于生物的对苯二甲酸和烯属单体的制备 - Google Patents
使基于生物的材料脱氧的方法以及基于生物的对苯二甲酸和烯属单体的制备 Download PDFInfo
- Publication number
- CN105264046B CN105264046B CN201480019619.5A CN201480019619A CN105264046B CN 105264046 B CN105264046 B CN 105264046B CN 201480019619 A CN201480019619 A CN 201480019619A CN 105264046 B CN105264046 B CN 105264046B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- deoxidation
- acid
- liquid
- hydrocarbon
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及使妥尔油沥青脱氧、得到脂族和芳族烃的方法。本发明甚至包括通过蒸汽裂化将脂族化合物转化为可聚合的烯烃,并且通过氧合和必要时的重排将芳族化合物转化为可聚合的对苯二甲酸。该单体可用于制备部分或完全生物来源的聚合物。根据本发明,首先加热妥尔油沥青以将它转化为液体,然后将其进料至催化剂床并且用氢气催化脱氧。脱氧催化剂优选为NiMo催化剂,且此外,可使用裂化催化剂,例如酸性沸石催化剂。使经脱氧的产物流冷却下来以获得液体,将该液体蒸馏以分离用于制备相应的单体和最终聚合物的脂族和芳族烃。
Description
本发明涉及使基于生物的材料脱氧的方法,所述基于生物的材料为含有相当大份额的脂肪酸和树脂酸和/或它们的衍生物、尤其是酯的妥尔油沥青。
本发明的进一步目的为用于由妥尔油沥青制备对苯二甲酸和制备烯属单体(如乙烯和丙烯)的方法,这些方法包括上述脱氧作为第一步骤。单体产物为用于制备生物聚合物如聚乙烯(PE)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二醇酯(PBT)的有用材料。
本发明甚至包括妥尔油沥青的用途以及上述中间单体产物用于制备生物聚合物PE、PP、PET和PBT的用途。
已经常规地由化石来源的原油制备聚合物。近来已经越来越多地研究由可再生原料制备的生物聚合物作为替代。一种这样的原料是作为来自纤维素浆蒸煮过程的副产物获得的妥尔油。
在WO2008/039756A1中描述了基于木材的材料裂化为石脑油沸点范围的液体。该方法的起始材料包括废的纤维素或木质素,将其浸在形成液体载体的妥尔油中。使用与沸石或二氧化硅-氧化铝催化剂(硅铝催化剂,silica alumina catalyst)组合的金属如Ni和Mo,使该淤浆经受催化加氢裂化过程。产物作为蒸汽获得,将所述蒸汽冷凝为液体,并且可将任何过量的氢气在该过程中循环。裂化从产物除去氧并且分子裂化为较小的分子。总的目的是制备燃料和化学中间产物,尽管还顺带提及用于制造塑料的单体。
妥尔油含有脂肪酸和树脂酸,可使其经受催化加氢脱氧(HDO)和裂化,得到带有烃的液态产物以及气体和水。液态烃已经被转化为生物燃料,但还有关于将其转化为单体化合物的文献,所述单体化合物可用作制备聚合物的起始材料。
WO2010/086507教导由至少75%的妥尔油脂肪酸和不超过25%的妥尔油树脂酸的蒸馏混合物制备可聚合的乙烯和丙烯的方法,使所述蒸馏混合物经受使用氢气的催化脱氧,随后使液态烃的产物经受蒸汽裂化,这得到所述单体。
WO2011/151528描述各种妥尔油材料如粗制妥尔油(CDO)、蒸馏的妥尔油(DTO)或妥尔油脂肪酸(TOFA)的催化加氢脱氧,随后从液态产物分离合适的芳族烃如对二甲苯或邻二甲苯并且将它们氧化为可用于制备生物来源的聚对苯二甲酸乙二醇酯(生物-PET)的对苯二甲酸。
不同于WO2010/086507的方法的WO2011/151528的方法的特征是它使用富含树脂酸的起始材料,其不能用作根据WO2010/086507的方法制备脂族烃和加氢裂化的烯烃的原料来源,并且甚至另外在其中是难以耐受的。为了增加产量,通常期望将起始材料的选择拓宽至粗制妥尔油或甚至在此之外,而非通过蒸馏纯化的酸。
US4,300,009在实施例18中描述了借助于氢气和沸石HZSM-5催化剂的妥尔油沥青的裂化,以该沥青的40%转化率得到烃。该结果表明没有实现所述沥青的基本脱氧。烃产物从剩余材料的分离也会是困难的。
本发明所要解决的问题是实现改进的方法,其容许使用新的和更便宜的原料以用于催化加氢脱氧以及获得可聚合化合物的后续工艺步骤,而无需蒸馏的或以其它方式纯化的妥尔油,不会劣化催化剂并且具有改进的得自脱氧步骤的脂族和芳族烃二者的产率。这将容许由单一丰富的原料来源并行制备聚烯烃和例如聚对苯二甲酸乙二醇酯。
本发明提供的解决方案是将妥尔油沥青用作用于该方法的基于生物的起始材料。因此,根据本发明的第一方面,提供使妥尔油沥青脱氧的方法,其中
-将含有一定份额(a share of)的脂肪酸和树脂酸和/或它们的衍生物的妥尔油沥青加热至足以将其变为液体的温度;
-将所述液体进料至催化剂床,以使其与氢气和一种或多种催化剂在所述催化剂床中接触;
-用氢气将该进料催化脱氧;和
-使来自所述床的气态流出物冷却下来,以得到液态产物,其包含脂族和芳族烃并且其已经是基本上完全脱氧的。
根据本发明的第二方面,提供制备基于生物的对苯二甲酸的方法,其中
-将含有一定份额的脂肪酸和树脂酸和/或它们的衍生物的妥尔油沥青加热至足以将其变为液体的温度;
-将所述液体进料至催化剂床,以使其与氢气和一种或多种催化剂在所述催化剂床中接触;
-用氢气将该进料催化脱氧;
-使来自所述床的气态流出物冷却下来,以得到液态中间产物,其包含脂族和芳族烃并且其已经是基本上完全脱氧的;
-将能转化为对苯二甲酸的芳族烃从所述中间产物分离;和
-使所分离的烃经受氧合和可能的重排反应,以使得对苯二甲酸作为最终产物获得。
根据本发明的第三方面,提供制备用于制备聚合物的烯属单体的方法,其中
-将含有一定份额的脂肪酸和树脂酸和/或它们的衍生物的妥尔油沥青加热至足以将其变为液体的温度;
-将所述液体进料至催化剂床,以使其与氢气和一种或多种催化剂在所述催化剂床中接触;
-用氢气将该进料催化脱氧;
-使来自所述床的气态流出物冷却下来,以得到液态中间产物,其包含脂族和芳族烃并且其已经是基本上完全脱氧的;
-将富含脂族烃的级分从所述中间产物分离;和
-使所述级分经受蒸汽裂化以获得含有可聚合烯烃的产物。
妥尔油沥青是固体级分,其作为来自粗制妥尔油的真空蒸馏或蒸汽蒸馏的不可蒸馏的残留物获得。妥尔油沥青的组成变化并且不能准确地限定,但是,游离的脂肪酸和树脂酸、酯化的脂肪酸和树脂酸、以及不能皂化(未皂化,unsaponifiable)的中性化合物(包括脂肪醇、二萜和甾醇)通常被报告为主要组分,脂肪酸和树脂酸以及它们的衍生物的份额为约40~90重量%并且萜烯的份额为约至多50重量%。对于组成,甚至参考Holblom等,Journal of the American Oil Chemists’Society,1978年3月,第55卷,第3期,第342-344页。妥尔油沥青可形成粗制妥尔油的至多40重量%并且已经被视为有限价值的废物。至今已发现它用作例如橡胶组分、柏油(asphalt)组分、表面活性剂、钻探泥浆组分和柏油(asphalt)粘合剂。然而,已经将大多数妥尔油沥青燃烧以作为能量的来源。
然而,妥尔油沥青的主要组分为与经蒸馏的妥尔油中的那些极为类似的游离的酸,或其密切相关的衍生物。妥尔油沥青特别富含松香酸、海松酸、油酸和亚油酸和它们的衍生物。其次,妥尔油沥青容易软化且通过温和加热至约55℃而变成液体,则可将其作为进料供给至加氢脱氧反应器,正如妥尔油可在室温下所做的那样。由于无论如何在反应器中的温度是高的(在300~450℃的范围内),所以只不过需要轻微加热来控制将它进料至该过程。已知用于使脂肪酸以及树脂酸脱氧和裂化(即,对于粗制妥尔油有效)的催化剂也可用于处理妥尔油沥青中的那些组分。
因而可将存在于妥尔油沥青中的树脂酸及其酯催化脱氧为单芳族化合物(monoaromate),例如与氢气处理相关的苯、甲苯和二甲苯。可通过分馏将适合用于生产对苯二甲酸的单芳族化合物(例如对二甲苯、间二甲苯、邻二甲苯、或对异丙基甲苯)从催化剂阶段的反应产物的液相分离。
单芳族化合物的分离和进一步加工是属于常规的石油化学的技术;因此,实践中易于实施根据本发明的方法。
根据本发明,可实现超过99%的妥尔油沥青的含氧组分转化为烃。所述烃产物将具有0.1%或更少的氧含量(从所述沥青中的约8.5~10%下降)。这样高的脱氧率对于所述产物成功地转化为烯烃或芳族单体来说是必要的。
在本发明中,可使用脱氧金属催化剂如NiMo或任选的包括金属和沸石催化剂的脱氧和裂化催化剂的组合,例如NiMo和ZSM-5的组合。要求是,与已经用作妥尔油脱氧的催化剂并且干扰该过程的酸性蒙脱石相反,在催化剂中不产生多环或沉积物。
金属催化剂可为预硫化的,例如具有NiMoS的形式,以便有效地除去存在于妥尔油沥青中的硫。因此可在该过程中实现90%的硫的除去。
催化加氢脱氧通过从脂肪酸释放氧并且形成水、一氧化碳和/或二氧化碳而工作。仍未发生碳链显著断裂成较小的分子,这对于芳族化合物(aromate)的收取是有利的。在本发明中,可将催化固定床的利用限制于脱氧阶段。
可将存在于妥尔油沥青中的脂肪酸及其酯催化脱氧为脂族化合物(aliphatics),其可通过蒸馏从液化产物分离并且通过常规的蒸汽裂化而变成烯属单体。
本发明的替代应用是脱氧之后在固定床中催化裂化以降低摩尔质量,由此脱氧和裂化阶段的催化剂彼此不同并且彼此分开地位于床中。裂化产生不饱和烃并且释放氢气,以使得优选将脱离它们的带有氢气的气体循环回到脱氧阶段。在那种情况下,甚至如下是可能的:该方法仅在初始阶段需要氢气的外部来源,并且此后简单地通过循环的氢气工作。
作为在固定床中的裂化的催化剂,可使用酸性催化剂,例如酸性沸石催化剂或蒙脱石催化剂。不考虑可能的催化裂化,作为脱氧阶段的催化剂,可使用金属催化剂例如NiMo或CoMo。后者用氢还原并且以公知的方式用硫化氢处理。在根据本发明的方法中,优选NiMo催化剂,因为它以高产率从CTO进料制备芳族化合物,但对焦化不敏感。
裂化阶段的催化剂优选为酸性的,如酸性沸石催化剂,优选ZSM-5催化剂。
借助于合适的催化剂,加氢脱氧和大量的催化裂化可同时在该床中发生。这样的催化剂包括带有镍的Y沸石(NiY沸石)或带有镍的蒙脱石(NiSMM),其需要在反应器中的高的氢气压力。NiSMM还使树脂酸裂化并且因此对于妥尔油组分的有效利用是特别有利的。
在加氢脱氧和可能的催化裂化阶段的合适的反应温度在300~450℃之内,优选320~430℃和最优选350~400℃。在较低的温度下存在聚合的风险,并且在较高的温度下存在焦化的风险;已经在将脂肪酸进料至反应器中时。为了避免焦化,优选的温度在320~400℃之内。有利地,可将温度升高以便在催化过程开始时在320~370℃之内并且在所述过程结束时在370~430℃之内。
在加氢脱氧和裂化阶段的合适的压力为50~100巴。处理优选持续30~60分钟、更优选35~50分钟。
在所述催化剂床中的重时空速(WHSV)优选为0.2~1.0升/小时。
关于对苯二甲酸的制备,这常规地由对二甲苯特别地通过氧化而获得。可将二甲苯的其它形式(间位和邻位)例如通过Henkel反应或其变型而转化为合适的。Henkel反应是工业规模的过程,其中使用热反应在金属盐如镉盐的存在下使芳族酸的碱金属盐重排(DE936036)。
根据优选的实施方式,根据本发明的方法通过经由如下来催化转化原料而进行:从反应产物的液相分离合适的二甲苯异构体,例如通过蒸馏,并且根据式1进行分离之后的阶段:
式1
可使用合适的化学或生物化学氧化剂、优选铬酸进行氧化。取决于所选择的二甲苯异构体,苯二甲酸(phthalic acid)或对苯二甲酸作为氧化的结果而获得。
将所获得的苯二甲酸(phthalic acid)通过Raecke(Hen-kel)重排反应转化为对苯二甲酸,该反应优选使用盐催化剂进行,在本发明中所述盐催化剂最优选包括钴镁盐。
根据Henkel重排反应,源材料酸的盐由源材料酸和盐催化剂形成,此后,将该源材料酸的盐加热至至少300℃、优选330~500℃、最优选350~450℃的温度,最适合在惰性气体气氛中。因此,获得对苯二甲酸的盐。
关于将对异丙基甲苯转化为对苯二甲酸,参考出版物Senseman,C.E.,Stubbs,J.J.,Ind.Eng.Chem.,1931,23(10),第1129页。
当需要时,所获得的对苯二甲酸可使用适合于该目的的任何醇如甲醇酯化,并且可将作为该反应的结果获得的对苯二甲酸二甲酯或相应的对苯二甲酸酯以公知的方式聚合为期望的聚酯。
相应地,基于生物的聚酯例如聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯可由根据本发明制备的基于生物的对苯二甲酸通过使它与基于生物的二醇聚合而生产。
可将根据本发明制备的基于生物的单体用于增加仍部分地基于化石原料的聚合物的生物单体部分,或可将那些基于生物的单体专门地用于制备完全基于生物的聚合物。
在下文中,参照附图(图1)更为具体地描述本发明,所述附图示意性地展示意图用于实施本发明的设备。
根据附图的妥尔油沥青的加氢脱氧和裂化过程的基本阶段为发生在立式反应器1中的催化脱氧和裂化阶段2、3,和从包括蒸馏4的这些阶段获得的液态烃的进一步处理以将它们分成脂族化合物(aliphate)和芳族化合物(aromate),所述脂族化合物和芳族化合物以它们各自的方式如石油化学领域中已知的那样进行处理。将可包含55~90重量%的游离的或酯化的脂肪酸和树脂酸的妥尔油沥青连同不能皂化(未皂化,unsaponifiable)的中性化合物一起进料至反应器1的上端。此外,将氢气从管线6供给至反应器1的上端。反应器1填充有作为床材料7工作的石英棉(quartz wool),其叠加的区域2、3彼此分开,具有用于使沥青进料的酸组分脱氧并且使进料脱硫的金属(例如,NiMo或NiMoS)催化剂和用于使碳链裂化的沸石或蒙脱土(montmorillonite)催化剂。反应器1中的液相和气相的流动方向是从顶部至底部。为了调节反应温度,反应器1设置有电热器8。
将通过反应器1的下端离开的热的反应产物引导至冷却器9,并且液化的产物通过管线10移动至分离槽11,分离槽11将水相12从油相13分离。使其主要组分为饱和的脂族烃以及芳族烃的油相13经受蒸馏4,其中收取芳族化合物A并且通过根据现有技术的方法将其进一步处理,且其中使脂族化合物14经受蒸汽裂化以获得低分子的烯烃。可通过使用已知的技术将所述烯烃转化为生物聚合物,例如聚乙烯或聚丙烯。将可被转化为对苯二甲酸的单芳族化合物从其它芳族化合物分离并且视需要通过氧合和重排进行处理。聚对苯二甲酸乙二醇酯通过采用二醇经由已知的方法聚合而获得。
在冷却器9中不冷凝并且含有氢气、碳的氧化物、可能的低分子烃和其它杂质的气体移动至纯化器15,纯化器15将氢气与其它气体组分分离。使纯的氢气通过管线16循环回到反应器1的上端以构成脱氧气体,并且从该过程除去碳的氧化物和其它杂质17。
实施例
将妥尔油沥青的样品用于测试。沥青进料的分析包括在以下表1中。倍半萜烯和萜烯醇难以彼此分离并且仅作为组呈现。沥青进料的元素分析见以下表2中。
进行如图1中所示的在反应器中的六小时的运行。将沥青通过加热熔融并且进料至用于脱氧和裂化的反应器。将氢气用作脱氧气体。脱氧催化剂为用H2S和H2在320℃下预硫化以形成NiMoS的NiMo。测试中初始的脱氧温度为约330℃并且朝着反应器的下端将其升高至约400℃。气体压力为约50巴。收集液体和气体产物,并且分析所述液体。在所述液体产物中发现的沥青进料的各组分的份额包括在表1中。所述液体产物的元素分析包括在表2中。
表1
表2
在进料中 | 在产物中 | ||||
碳 | C | % | ASTM D 5373 | 79.8 | 85.7 |
氢 | H | % | ASTM D 5373 | 10.8 | 13 |
氮 | N | % | ASTM D 5373 | <0.1 | <0.1 |
钠 | Na | mg/kg | 湿式燃烧+ICP-OES | 810 | <5 |
钾 | K | mg/kg | 湿式燃烧+ICP-OES | 82 | <5 |
硫 | S | mg/kg | 湿式燃烧+ICP-OES | 3100 | 270 |
磷 | P | mg/kg | 湿式燃烧+ICP-OES | 56 | <5 |
铁 | Fe | mg/kg | 湿式燃烧+ICP-OES | 17 | <1 |
钙 | Ca | mg/kg | 湿式燃烧+ICP-OES | 73 | <5 |
所述液体产物的大部分由烃形成。N-烷烃、环烷和芳族化合物在产物中的份额分别为48.1重量%、47.5重量%和4.3重量%。所述产物特别富含十八烷和十七烷,它们的份额分别为22.5重量%和16.7重量%。
结果表明妥尔油沥青可有效地用于制备不含氧的液态烃。该方法除去超过99%、甚至超过99.9%的包含在沥青进料中的氧,并且甚至从液体产物除去沥青的钠内容物的超过90%。所得的液态烃能通过蒸馏而分离成主要的脂族级分和次要的芳族级分,前者能通过加氢裂化转化为烯烃并且后者能如上所述通过已知的方式转化为对苯二甲酸。
Claims (27)
1.使妥尔油沥青脱氧的方法,其中
-将含有一定份额的脂肪酸和树脂酸和/或它们的衍生物的妥尔油沥青加热至足以将其变为液体的温度;
-将所述液体进料至催化剂床(7),以使其与氢气和一种或多种催化剂(2、3)在所述催化剂床中接触,所述催化剂包括NiMo脱氧催化剂(2);
-用氢气将进料催化脱氧;和
-使来自所述床的气态流出物冷却下来,以得到液态产物(10),其包含脂族和芳族烃并且其已经是脱氧的。
2.权利要求1的方法,特征在于将妥尔油沥青加热至至少55℃的温度。
3.权利要求1或2的方法,特征在于将所述液态产物分成富含脂族烃的级分和富含芳族烃的级分。
4.权利要求1或2的方法,特征在于使用脱氧催化剂(2)和裂化催化剂(3),这两种催化剂彼此不同并且顺序地彼此分开地位于由固体床材料形成的所述催化剂床(7)中。
5.权利要求1或2的方法,特征在于脱氧阶段的所述催化剂(2)是包含NiMoS的催化剂。
6.权利要求4的方法,特征在于裂化阶段的所述催化剂(3)是酸性的。
7.权利要求6的方法,特征在于裂化阶段的所述催化剂(3)是酸性沸石催化剂。
8.权利要求6的方法,特征在于裂化阶段的所述催化剂(3)是ZSM-5催化剂。
9.权利要求1或2的方法,特征在于所述脱氧在300~450℃的温度下进行。
10.权利要求9的方法,特征在于通过升高温度以在所述催化脱氧过程开始时在320~370℃之内和在所述催化脱氧过程结束时在370~430℃之内进行所述脱氧。
11.权利要求1或2的方法,特征在于所述脱氧在50~100巴的压力下进行。
12.权利要求1或2的方法,特征在于在所述催化剂床中的重时空速(WHSV)为0.2~1.0/小时。
13.权利要求1或2的方法,特征在于将包含在所述液态产物(10)中的水(12)从所制备的液态烃分离。
14.权利要求13的方法,特征在于将一种或多种能转化为对苯二甲酸的芳族烃通过蒸馏从所述液态烃分离。
15.权利要求13的方法,特征在于从所述液态烃分离的所述芳族烃是邻二甲苯、间二甲苯或对二甲苯、或者异丙基甲苯。
16.权利要求15的方法,特征在于所述异丙基甲苯为对异丙基甲苯。
17.制备基于生物的对苯二甲酸的方法,其中
-将含有一定份额的脂肪酸和树脂酸和/或它们的衍生物的妥尔油沥青加热至足以将其变为液体的温度;
-将所述液体进料至催化剂床(7),以使其与氢气和一种或多种催化剂(2、3)在所述催化剂床中接触,所述催化剂包括NiMo脱氧催化剂(2);
-用氢气将进料催化脱氧;
-使来自所述床的气态流出物冷却下来,以得到液态中间产物,其包含脂族和芳族烃并且其已经是脱氧的;
-将能转化为对苯二甲酸的芳族烃从所述中间产物分离;和
-使所分离的烃经受氧合和可能的重排反应,以使得对苯二甲酸作为最终产物获得。
18.权利要求17的方法,特征在于所分离的烃的氧合是使用化学或生物化学氧化剂进行的。
19.权利要求18的方法,特征在于所分离的烃的氧合是使用铬酸进行的。
20.权利要求17或18的方法,特征在于将对二甲苯从所述中间产物分离并且氧化为对苯二甲酸。
21.权利要求17或18的方法,特征在于将邻二甲苯从所述中间产物分离并且氧化为苯二甲酸,此后,将其通过Raecke或Henkel重排反应转化为对苯二甲酸。
22.权利要求21的方法,特征在于将邻二甲苯从所述中间产物分离并且氧化为苯二甲酸,此后,将其通过Raecke或Henkel重排反应转化为对苯二甲酸,使用盐催化剂。
23.权利要求21的方法,特征在于将邻二甲苯从所述中间产物分离并且氧化为苯二甲酸,此后,将其通过Raecke或Henkel重排反应转化为对苯二甲酸,使用钴-镁盐催化剂。
24.权利要求17或18的方法,特征在于在所述重排中,将反应混合物在惰性气体气氛中加热至至少300℃的温度。
25.权利要求24的方法,特征在于在所述重排中,将反应混合物在惰性气体气氛中加热至330~500℃的温度。
26.制备用于制备聚合物的烯属单体的方法,其中
-将含有一定份额的脂肪酸和树脂酸和/或它们的衍生物的妥尔油沥青加热至足以将其变为液体的温度;
-将所述液体进料至催化剂床(7),以使其与氢气和一种或多种催化剂(2、3)在所述催化剂床中接触,所述催化剂包括NiMo脱氧催化剂(2);
-用氢气将进料催化脱氧;
-使来自所述床的气态流出物冷却下来,以得到液态中间产物(10),其包含脂族和芳族烃并且其已经是脱氧的;
-将富含脂族烃的级分(14)从所述中间产物分离;和
-使所述级分(14)经受蒸汽裂化以获得含有可聚合烯烃的产物。
27.权利要求26的方法,特征在于通过所述蒸汽裂化制备乙烯和/或丙烯。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20135342A FI125589B2 (en) | 2013-04-08 | 2013-04-08 | Processes for deoxidation of bio-based materials and production of bio-based terephthalic acid and olefinic monomers |
FI20135342 | 2013-04-08 | ||
PCT/FI2014/050251 WO2014167181A1 (en) | 2013-04-08 | 2014-04-08 | Methods of deoxygenating bio-based material and production of bio-based terephtalic acid and olefinic monomers |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105264046A CN105264046A (zh) | 2016-01-20 |
CN105264046B true CN105264046B (zh) | 2018-06-26 |
Family
ID=51688997
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480019619.5A Active CN105264046B (zh) | 2013-04-08 | 2014-04-08 | 使基于生物的材料脱氧的方法以及基于生物的对苯二甲酸和烯属单体的制备 |
Country Status (9)
Country | Link |
---|---|
US (1) | US11525094B2 (zh) |
EP (1) | EP2984154B1 (zh) |
CN (1) | CN105264046B (zh) |
BR (1) | BR112015025645B1 (zh) |
CA (1) | CA2907844C (zh) |
FI (1) | FI125589B2 (zh) |
PL (1) | PL2984154T3 (zh) |
RU (1) | RU2664547C2 (zh) |
WO (1) | WO2014167181A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK3421572T3 (da) | 2017-06-29 | 2020-11-09 | Neste Oyj | Fremgangsmåde til øgning af benzin- og middeldestillatselektivitet ved katalytisk krakning |
CN109705985A (zh) * | 2017-10-25 | 2019-05-03 | 中国科学院大连化学物理研究所 | 一种pet、ptt、pbt制造物转化为航空煤油范围环烃的方法 |
JP7271541B2 (ja) * | 2017-11-21 | 2023-05-11 | サンパイン アーベー | トール油ピッチ(top)の熱処理方法 |
FI127783B (en) * | 2017-11-27 | 2019-02-28 | Neste Oyj | Manufacture of a mixture of fuels |
FI130603B (en) * | 2018-08-03 | 2023-12-08 | Neste Oyj | THE METHOD PRODUCES BIORENEWABLE PROPENE FROM OILS AND FATS |
FI129886B (fi) * | 2020-12-18 | 2022-10-14 | Neste Oyj | Meriliikenteen uusiutuvan polttoaineen koostumukset ja menetelmät sen valmistamiseksi |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4300009A (en) * | 1978-12-28 | 1981-11-10 | Mobil Oil Corporation | Conversion of biological material to liquid fuels |
WO2010086507A1 (en) * | 2009-01-29 | 2010-08-05 | Stora Enso Oyj | Method for producing olefinic monomers from bio oil |
WO2012062924A1 (en) * | 2010-11-12 | 2012-05-18 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of a biofuel and/or biochemical |
CN103025851A (zh) * | 2010-06-03 | 2013-04-03 | 斯塔诺阿埃索澳吉有限公司 | 用于制备芳族单体的不纯妥尔油的氢处理 |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE936036C (de) | 1952-11-21 | 1955-12-01 | Henkel & Cie Gmbh | Verfahren zur Herstellung von Terephthalsaeure |
US2894880A (en) | 1955-09-12 | 1959-07-14 | Heyden Newport Chemical Corp | Method of fractionating tall oil into fatty acids and rosin acid products |
US2857331A (en) * | 1955-12-12 | 1958-10-21 | Smith Douglass Company Inc | Flotation reagent |
US3649580A (en) * | 1969-03-13 | 1972-03-14 | Arizona Chem | Tall oil pitch tackifiers in ethylene-propylene terpolymer rubber |
US4357145A (en) * | 1981-03-27 | 1982-11-02 | Dondelewski Michael A | Carbonaceous pellets and method of making |
US4337193A (en) | 1981-04-27 | 1982-06-29 | Arizona Chemical Company | Preparation of hardened tall oil pitch |
DE3407925C1 (de) * | 1984-03-03 | 1985-09-05 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur Herstellung von Terephthalsaeuredimethylester aus p-Xylol und Methanol |
CA1301371C (en) | 1988-08-23 | 1992-05-19 | Jan Erik Aune | Log scanner |
NZ245399A (en) | 1993-01-14 | 1995-05-26 | Interpine Export Nz Ltd | Portable computerised log measurer |
US6463402B1 (en) | 2000-03-06 | 2002-10-08 | Ralph W. Bennett | Infeed log scanning for lumber optimization |
RU2177954C1 (ru) * | 2001-02-12 | 2002-01-10 | Казанское открытое акционерное общество "Органический синтез" | Способ получения полиэтилена низкого давления |
US6778681B2 (en) | 2001-05-09 | 2004-08-17 | Invision Technologies, Inc. | Analysis and presentation of internal features of logs |
US6690990B1 (en) | 2002-12-02 | 2004-02-10 | CENTRE DE RECHERCHE INDUSTRIELLE DU QUéBEC | Method of optimizing a layout of selected parts to be cut |
FI20031390A0 (fi) | 2003-09-26 | 2003-09-26 | Raute Oyj | Menetelmä viilusaannon optimoimiseksi viilusorvauksessa |
US8662121B2 (en) | 2006-03-30 | 2014-03-04 | Weyerhaeuser Nr Company | Method for reducing warp potential within lumber derived from a raw material |
US20080015711A1 (en) | 2006-06-27 | 2008-01-17 | Normand Charland | Systems and methods for forest harvest management |
US7994375B2 (en) | 2006-09-26 | 2011-08-09 | Uop Llc | Production of gasoline, diesel, naphthenes and aromatics from lignin and cellulosic waste by one step hydrocracking |
US7846323B2 (en) | 2007-04-06 | 2010-12-07 | Syntroleum Corporation | Process for co-producing jet fuel and LPG from renewable sources |
FR2917424B1 (fr) | 2007-06-12 | 2012-10-19 | Inst Francais Du Petrole | Production de charges de vapocraquage a haut rendement en ethylene, propylene et polymeres resultants par hydrotraitement d'huile vegetales |
US8346631B2 (en) | 2007-10-16 | 2013-01-01 | Eb Associates, Inc. | Systems and methods for tracking lumber in a sawmill |
AU2009233957B2 (en) * | 2008-04-06 | 2013-09-26 | Battelle Memorial Institute | Fuel and fuel blending components from biomass derived pyrolysis oil |
BRPI0802222B1 (pt) | 2008-06-03 | 2022-01-04 | Petróleo Brasileiro S.A. - Petrobras | Processo para produzir olefinas leves a partir de uma carga contendo triglicerídeos |
US7968757B2 (en) * | 2008-08-21 | 2011-06-28 | Syntroleum Corporation | Hydrocracking process for biological feedstocks and hydrocarbons produced therefrom |
EP2290035A1 (en) | 2009-07-27 | 2011-03-02 | Total Petrochemicals Research Feluy | A process for the production of bio-naptha from complex mixtures of natural occurring fats and oils |
AU2010313862B2 (en) | 2009-10-27 | 2014-10-23 | Ignite Resources Pty Ltd | Methods for producing hydrocarbon products from bio-oils and/or coal -oils |
FI126337B (fi) * | 2010-03-26 | 2016-10-14 | Forchem Oy | Menetelmä mäntyöljypien hyödyntämiseksi |
-
2013
- 2013-04-08 FI FI20135342A patent/FI125589B2/en active IP Right Grant
-
2014
- 2014-04-08 BR BR112015025645-7A patent/BR112015025645B1/pt active IP Right Grant
- 2014-04-08 CA CA2907844A patent/CA2907844C/en active Active
- 2014-04-08 RU RU2015147554A patent/RU2664547C2/ru active
- 2014-04-08 US US14/782,879 patent/US11525094B2/en active Active
- 2014-04-08 EP EP14782419.7A patent/EP2984154B1/en active Active
- 2014-04-08 PL PL14782419T patent/PL2984154T3/pl unknown
- 2014-04-08 WO PCT/FI2014/050251 patent/WO2014167181A1/en active Application Filing
- 2014-04-08 CN CN201480019619.5A patent/CN105264046B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4300009A (en) * | 1978-12-28 | 1981-11-10 | Mobil Oil Corporation | Conversion of biological material to liquid fuels |
WO2010086507A1 (en) * | 2009-01-29 | 2010-08-05 | Stora Enso Oyj | Method for producing olefinic monomers from bio oil |
CN103025851A (zh) * | 2010-06-03 | 2013-04-03 | 斯塔诺阿埃索澳吉有限公司 | 用于制备芳族单体的不纯妥尔油的氢处理 |
WO2012062924A1 (en) * | 2010-11-12 | 2012-05-18 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of a biofuel and/or biochemical |
Also Published As
Publication number | Publication date |
---|---|
PL2984154T3 (pl) | 2018-09-28 |
US20160046873A1 (en) | 2016-02-18 |
RU2015147554A (ru) | 2017-05-11 |
BR112015025645B1 (pt) | 2020-11-10 |
CN105264046A (zh) | 2016-01-20 |
BR112015025645A2 (pt) | 2017-07-18 |
FI20135342A (fi) | 2014-10-09 |
CA2907844A1 (en) | 2014-10-16 |
CA2907844C (en) | 2020-11-24 |
WO2014167181A1 (en) | 2014-10-16 |
EP2984154A1 (en) | 2016-02-17 |
FI125589B2 (en) | 2022-03-31 |
US11525094B2 (en) | 2022-12-13 |
RU2015147554A3 (zh) | 2018-03-26 |
EP2984154B1 (en) | 2018-05-30 |
RU2664547C2 (ru) | 2018-08-20 |
EP2984154A4 (en) | 2016-11-09 |
FI125589B (en) | 2015-12-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105264046B (zh) | 使基于生物的材料脱氧的方法以及基于生物的对苯二甲酸和烯属单体的制备 | |
JP6360554B2 (ja) | 水蒸気分解ユニットにおいて炭化水素原料を分解する方法 | |
DK3058050T3 (en) | PROCEDURE FOR THE PREPARATION OF CARBON HYDRADES OF RAW TALL OIL AND TALL OIL CUP | |
FI127333B (en) | Process for the preparation of hydrocarbons | |
FI121626B (fi) | Menetelmä olefiinisten monomeerien tuottamiseksi | |
RU2569897C2 (ru) | Водородная обработка неочищенного талового масла для получения ароматических мономеров | |
ES2372926T3 (es) | Proceso para producir olefinas ligeras a partir de una alimentación que contiene triglicéridos. | |
JP2017511829A (ja) | 高沸点炭化水素供給原料をより軽沸点の炭化水素生成物へ転換する方法 | |
RU2618234C2 (ru) | Способы деоксигенации таллового масла и получения из него полимеризуемых мономеров | |
CN104302736B (zh) | 妥尔油脱氧的方法和由其制备可聚合单体的方法 | |
FI125561B (en) | Hydrogen treatment of impure tall oil to produce aromatic monomers | |
EP4240811A1 (en) | Process for manufacturing bio-based hydrocarbons and bio-gasoline composition | |
WO2013029663A1 (en) | Method for hydroisomerising renewable hydrocarbons |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |