CN105189722A - Diene-selective hydrogenation of metathesis-derived olefins and unsaturated esters - Google Patents

Diene-selective hydrogenation of metathesis-derived olefins and unsaturated esters Download PDF

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Publication number
CN105189722A
CN105189722A CN201480015348.6A CN201480015348A CN105189722A CN 105189722 A CN105189722 A CN 105189722A CN 201480015348 A CN201480015348 A CN 201480015348A CN 105189722 A CN105189722 A CN 105189722A
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Prior art keywords
hydrogenation
ester
metal
alkene
metathesis
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CN201480015348.6A
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Chinese (zh)
Inventor
L.A.孔兹
T.M.帕尔斯
S.A.科恩
M.L.利特肯斯
C.巴拉克里施南
R.B.施奈德
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Fung Yip Trading Pte Ltd
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Ai Laiwansi Renewable Energy Source Science Limited-Liability Co
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Priority claimed from US13/827,153 external-priority patent/US9051519B2/en
Application filed by Ai Laiwansi Renewable Energy Source Science Limited-Liability Co filed Critical Ai Laiwansi Renewable Energy Source Science Limited-Liability Co
Publication of CN105189722A publication Critical patent/CN105189722A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B11/00—Recovery or refining of other fatty substances, e.g. lanolin or waxes
    • 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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/002—Sources of fatty acids, e.g. natural glycerides, characterised by the nature, the quantities or the distribution of said acids
    • 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
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • 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
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
    • 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
    • C11C3/14—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by isomerisation

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Methods are provided for refining natural oil feedstocks and partially hydrogenating polyunsaturated olefins and polyunsaturated esters. The methods comprise reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters. In certain embodiments, the methods further comprise separating the polyunsaturated olefins from the polyunsaturated esters in the metathesized product. In certain embodiments, the methods further comprise partially hydrogenating the polyunsaturated olefins in the presence of a hydrogenation catalyst, wherein at least a portion of the polyunsaturated olefins are converted to monounsaturated olefins. In other embodiments, the methods further comprise partially hydrogenating the polyunsaturated esters in the presence of a hydrogenation catalyst, wherein at least a portion of the polyunsaturated esters are converted to monounsaturated esters.

Description

The diene selective hydration of the alkene that metathesis obtains and unsaturated ester
The cross reference of related application
This application claims the benefit of priority of the U.S. Patent Application No. 13/827,153 that on March 14th, 2013 submits to, its full content is incorporated herein by reference, as set forth completely in this article.
Background technology
Metathesis (transposition, metathesis) be the usually known catalyzed reaction in this area, it relates to the exchange via the formation of carbon-to-carbon double bond and alkylidene group (alkylidene) unit of fracture between the compound (such as, olefinic compounds) containing one or more double bond.Metathesis can betide between two same molecules (being commonly called self-metathesis), and/or it can betide between two different molecules (being commonly called cross metathesis).Self-metathesis can schematically represent as shown in equation I:
Wherein R 1and R 2for organic group.
Cross metathesis can schematically represent as shown in equation II:
R 1-CH＝CH-R 3+R 1-CH＝CH-R 4+R 2-CH＝CH-R 3+R 2-CH＝CH-R 4
+R 1-CH＝CH-R 1+R 2-CH＝CH-R 2+R 3-CH＝CH-R 3+R 4-CH＝CH-R 4
Wherein R 1, R 2, R 3and R 4for organic group.
In recent years, to manufacturing the demand sustainable growth typically deriving from the environmentally friendly technology of the material of petroleum resources.Such as, researchist is studying the feasibility using natural oil raw material such as to manufacture biofuel, wax, plastics etc. based on the oil of Plants and Seeds always.In a limiting examples, metathesis catalyst is for the manufacture of candle wax, and as described in PCT/US2006/000822, its full content is incorporated herein by reference.The replacement(metathesis)reaction relating to natural oil raw material is current and will provide solution likely future.
Interested natural oil raw material comprises the derivative such as lipid acid and fatty acid alkyl ester (such as, methyl esters) of limiting examples such as natural oil (such as, vegetables oil, fish oil, animal tallow) and natural oil.These raw materials change into industrial useful chemical (such as wax, plastics, makeup, biofuel etc.) by many different replacement(metathesis)reactions.As limiting examples, significant reactive species comprises self-metathesis, reacts with the cross metathesis of alkene and ring-opening methathesis.The representative limiting examples of the metathesis catalyst provided below.Metathesis catalyst can be expensive, therefore expects the effect improving metathesis catalyst.
In recent years, to the demand sustainable growth of the transport fuel based on gasoline.There is following concern: world oil output can catch up with demand.In addition, the increase in demand of the fuel based on oil has been caused to the higher generation of greenhouse gases.Particularly, in the U.S., air system accounts for the greenhouse gases exceeding and be greater than 10%.Due to the increase produced increase and the greenhouse gases of demand for fuel, need to develop the method for originating for the manufacture of eco-friendly alternative fuel.Particularly, exploitation is needed to be used for from the fuel composition of natural matter manufacturing environment close friend and the method for specialty chemicals that comprise cholesterol olefin(e) compound.
Summary of the invention
Disclose under the existence of metathesis catalyst by the method for the replacement(metathesis)reaction of natural oil raw material from natural oil raw material refining cholesterol olefin(e) compound.
In one embodiment, the method comprises provides the raw material that comprises natural oil and makes raw material react to form the metathesis product comprising many unsaturated olefins and many unsaturated ester under the existence of metathesis catalyst in double decomposition reactor.The method comprises further by many unsaturated olefins and/or the partly hydrogenation in the presence of a hydrogenation catalyst of many unsaturated ester, and wherein many unsaturated olefins and/or many unsaturated ester are converted into cholesterol alkene and/or cholesterol ester at least partially.In some embodiments, the many unsaturated olefins in metathesis product are separated with the many unsaturated ester in metathesis product before being included in step of hydrogenation further by the method.In other embodiments, after the separation step and before step of hydrogenation, the method comprises carries out transesterify to form ester exchange offspring in the presence of an alcohol by many unsaturated ester.In other substituting embodiments, after separating step and step of hydrogenation, cholesterol ester is carried out in the presence of an alcohol transesterify to form ester exchange offspring.
In some embodiments, many unsaturated olefins are converted into cholesterol alkene at least partially, and transformation efficiency can be at least 85%, 90% or 95%; And selectivity can be at least 90%, 95% or 99%.In other embodiments, many unsaturated ester are converted into cholesterol ester at least partially, and transformation efficiency can be at least 85%, 90% or 95%; And selectivity can be at least 90%, 95% or 99%.In some embodiments, many unsaturated olefins are converted into cholesterol alkene and many unsaturated ester are converted into cholesterol ester at least partially at least partially.
In some embodiments, hydrogenation catalyst comprises the metal being selected from nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium and combination thereof.Hydrogenation catalyst can the amount of 0.01-1.0 % by weight of many unsaturated olefins and/or many unsaturated ester provide.Step of hydrogenation can carry out 30-180 minute with the hydrogen pressure of 50psig-500psig at the temperature of 150 DEG C-250 DEG C.In some embodiments, hydrogenation catalyst recirculation before step of hydrogenation.
In some embodiments, the method is included in further and makes before raw material reacts under the existence of metathesis catalyst, under the condition being enough to the catalyzer poison reduced in raw material, to process raw material.In some embodiments, this treatment step relates to and carries out chemical treatment to reduce catalyzer poison by chemical reaction.In other embodiments, this treatment step relates to and processes raw material with following one or more: heat, molecular sieve, aluminum oxide, silica gel, illiteracy take off (stone) clay, Fuller's earth, bleaching clay, diatomite, zeolite, kaolin, activated metal, acid anhydrides, gac, SODA ASH LIGHT 99.2, metal hydride, metal sulfate, metal halide, metal carbonate, metal silicate, Vanadium Pentoxide in FLAKES, metal alanates, alkyl aluminum hydride, metal borohydride, organometallic reagent, carbon carry palladium (palladium charcoal) catalyzer and combination thereof.In other embodiment again, raw material is not being deposited the temperature that is heated in the case of oxygen be greater than 100 DEG C and kept time of being enough to reduce catalyzer poison at such a temperature.
In some embodiments, the method comprises further provides low molecular weight olefins or middle-molecular-weihydroxyethyl alkene (mid-weightolefin), and wherein reactions steps comprises the cross-metathesis between raw material and low molecular weight olefins or middle-molecular-weihydroxyethyl alkene.
In another embodiment, the method comprises the raw material providing and comprise many unsaturated olefins and the hydrogen pressure partly hydrogenation 30-180 minute many unsaturated olefins being used in the presence of a hydrogenation catalyst at the temperature of 150 DEG C-250 DEG C 50psig-500psig, wherein hydrogenation catalyst provides with the amount of the 0.01-1.0 % by weight of many unsaturated olefins, and wherein step of hydrogenation has the transformation efficiency of at least 85% and the selectivity of at least 90%.In some embodiments, before step of hydrogenation, under the condition being enough to the catalyzer poison reduced in raw material, raw material is processed.In other embodiments, hydrogenation catalyst comprises the metal being selected from nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium and combination thereof.In some embodiments, transformation efficiency is at least 90% and selectivity is at least 95%.In other embodiments, transformation efficiency is at least 95% and selectivity is at least 99%.In other embodiment again, hydrogenation catalyst is recirculation before step of hydrogenation.
In another embodiment, the method comprises the raw material providing and comprise many unsaturated ester and the hydrogen pressure partly hydrogenation 30-180 minute many unsaturated ester being used in the presence of a hydrogenation catalyst at the temperature of 150 DEG C-250 DEG C 50psig-500psig, wherein hydrogenation catalyst provides with the amount of the 0.01-1.0 % by weight of many unsaturated ester, and wherein step of hydrogenation has the transformation efficiency of at least 85% and the selectivity of at least 90%.In some embodiments, before step of hydrogenation, under the condition being enough to the catalyzer poison reduced in raw material, raw material is processed.In other embodiments, hydrogenation catalyst comprises the metal being selected from nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium and combination thereof.In some embodiments, transformation efficiency is at least 90% and selectivity is at least 95%.In other embodiments, transformation efficiency is at least 95% and selectivity is at least 99%.In other embodiment again, hydrogenation catalyst is recirculation before step of hydrogenation.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the embodiment manufacturing the method for fuel composition and ester exchange offspring from natural oil.
Embodiment
As used in this article, singulative " indefinite article one (kind) (a, an) " and " definite article is somebody's turn to do (described) (the) " comprise plural reference, unless context is clearly otherwise noted.Such as, mention that " substituting group " comprises single substituting group and two or more substituting groups etc.
As used in this article, term " such as (forexample) ", " such as (forinstance) ", " such as (suchas) " or " comprising " are intended to introduce the example of illustrating more general theme further.Unless otherwise prescribed, these examples only provide as understanding the supplementary means applied shown in present disclosure, and are not intended to by any way for restrictive.
As used in this article, following term has following implication, unless described on the contrary clearly.Should be understood that the term of any singulative can comprise its plural counterpart, vice versa.
As used in this article, term " metathesis catalyst " comprises catalyzer or the catalyst system of any catalysed metathesis reaction.
As used in this article, term " natural oil ", " natural matter " or " natural oil raw material " can refer to the oil deriving from plant or animal-origin.Term " natural oil " comprises natural oil derivatives, except as otherwise noted.This term also comprises modified plant or animal-origin (such as, (genetically modified) plant of genetic modification or animal-origin), except as otherwise noted.The example of natural oil includes, but not limited to vegetables oil, algae oil, fish oil, animal tallow, Yatall MA, the derivative of these oil, any combination etc. of these oil.The representative limiting examples of vegetables oil comprises mustard caul-fat, rapeseed oil, Oleum Cocois, Semen Maydis oil, Oleum Gossypii semen, sweet oil, plam oil, peanut oil, Thistle oil, sesame oil, soybean oil, Trisun Oil R 80, Toenol 1140, palm-kernel oil, tung oil, curcas oil (jatropha oil), tori seed oil, Thlaspi oil, false flax oil and Viscotrol C.The representative limiting examples of animal tallow comprises lard, tallow, fowl fat, yellow fat and fish oil.Yatall MA is the by product that wood pulp manufactures.
As used in this article, what term " natural oil derivatives " can refer to use any one or combination of methods known in the art derives from the compound of natural oil or the mixture of compound.Such method includes, but not limited to saponification, steatolysis, transesterify, esterification, hydrogenation (partly, selectivity or complete), isomerization, oxidation and reduction.The representative limiting examples of natural oil derivatives comprises natural gum, phosphatide, soap stock (soap stock), acidifying soap stock, distillment (overhead product) or distills its hydroxyl replacement variant of sludge, lipid acid and fatty acid alkyl ester (such as, limiting examples such as 2-(ethyl hexyl) ester), natural oil.Such as, natural oil derivatives can be the fatty acid methyl ester (" FAME ") of the glyceryl ester deriving from natural oil.In some embodiments, raw material comprises mustard caul-fat or soybean oil, as limiting examples, through the soybean oil (that is, RBD soybean oil) of refining, decolouring and deodorization.Soybean oil typically comprises the triglyceride level of the lipid acid of about 95% weight or higher (such as, 99% weight or higher).Main lipid acid in the polyol ester of soybean oil comprises: saturated fatty acid, as limiting examples, and palmitinic acid (hexadecanoic acid) and stearic acid (octadecanoic acid); And unsaturated fatty acids, as limiting examples, be oleic acid (9-octadecenoic acid), linolic acid (9,12 octadecadienoic acid) and linolenic acid (cis 9,12,15-oc-tadecatrienoic acid).
As used in this article, term " metathesis " can refer to that raw material reacts to be formed the metathesis product comprising new olefinic compounds under the existence of metathesis catalyst.Metathesis can refer to cross metathesis (also referred to as common metathesis), self-metathesis, ring-opening methathesis, ring opening metathesis polymerization (" ROMP "), Ring-closing metathesis (" RCM ") and acyclic dienes metathesis (" ADMET ").As limiting examples, metathesis can refer to two triglyceride level reaction (self-metathesis) making to exist in natural matter under the existence of metathesis catalyst, wherein each triglyceride level has unsaturated carbon-to-carbon double bond, forms the mixture of new alkene and ester (it can comprise triglyceride level dimer) thus.Such triglyceride level dimer can have more than one olefinic bonds, therefore also can form more senior oligopolymer.In addition, metathesis can instigate the triglyceride level in alkene (such as ethene) and natural matter with at least one unsaturated carbon-to-carbon double bond to react, and forms new olefinic molecule and new ester molecule (cross metathesis) thus.
As used in this article, term " ester " can refer to the compound with general formula R-COO-R ', wherein R and R ' represents any organic compound (such as alkyl, aryl or silyl), comprises those (comprise carry and comprise heteroatomic substituted radical those) of carrying heteroatoms and comprising substituted radical.In some embodiments, R and R ' represents alkyl, thiazolinyl, aryl or alcohol radical.In some embodiments, term " ester " can refer to one group of compound with above-mentioned general formula, and wherein compound has different carbon length.
As used in this article, term " dibasic ester (diester) " can refer to have general formula R '-OOC-Y-COO-R " compound; wherein Y, R ' and R " represent any organic compound (such as alkyl, aryl or silyl), comprise those (comprise carry and comprise heteroatomic substituted radical those) of carrying heteroatoms and comprising substituted radical.In some embodiments, Y is saturated or undersaturated hydrocarbon, and R ' and R " be alkyl, thiazolinyl, aryl or alcohol radical.
As used in this article, term " diprotic acid " can refer to have general formula R '-OOC-Y-COO-R " compound; wherein R ' and R " be hydrogen, and Y represents any organic compound (such as alkyl, thiazolinyl, aryl, alcohol radical or silyl), comprise those that carry hybrid atom MCM-41 group.In some embodiments, Y is saturated or undersaturated hydrocarbon.
As used in this article, term " alkene " can refer to the hydrocarbon compound with at least one unsaturated carbon-to-carbon double bond.In some embodiments, term " alkene " can refer to one group of unsaturated carbon-carbon double bond compound with different carbon length.Unless otherwise, term " alkene " is contained " many unsaturated olefins " or " many-alkene " with more than one carbon-to-carbon double bond.
As used in this article, term " cholesterol alkene " or " mono-olefins " refer to the hydrocarbon compound only with a carbon-to-carbon double bond.
Note, if R or the R ' group in general formula R-COO-R ' contains unsaturated carbon-to-carbon double bond, then alkene (comprising mono-olefins and many-both alkene) also can comprise ester, and ester also can comprise alkene.Such as, " terminal olefine ester " can refer to that wherein R has the ester cpds of the alkene being positioned at chain end." internal olefin ester " can refer to that wherein R has the ester cpds of the alkene of the interior location being positioned at chain.In addition, term " terminal olefine " can refer to that wherein R ' represents hydrogen or any organic compound (such as alkyl, aryl, thiazolinyl, alcohol radical or silyl) and R has ester or its acid of the alkene being positioned at chain end, and term " internal olefin " can refer to that wherein R ' represents hydrogen or any organic compound (such as alkyl, aryl, thiazolinyl, alcohol radical or silyl) and R has ester or its acid of the alkene of the interior location being positioned at chain.
As used in this article, term " low molecular weight olefins " can refer to any one or combination of undersaturated straight chain, side chain or cyclic hydrocarbon within the scope of C2-C14.Low molecular weight olefins comprises " alpha-olefin " or " terminal olefine ", and wherein unsaturated C-C is present in an end of compound.Low molecular weight olefins also can comprise diene or triolefin.Low molecular weight olefins also can comprise internal olefin or " lower molecular weight internal olefin ".In some embodiments, lower molecular weight internal olefin is within the scope of C4-C14.The example of the low molecular weight olefins within the scope of C2-C6 comprises, but be not limited to: ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 3-amylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentenes, Isosorbide-5-Nitrae-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-amylene, 3-methyl-2-amylene, 4-methyl-2-amylene, 2-methyl-3-amylene and tetrahydrobenzene.The limiting examples of the low molecular weight olefins within the scope of C7-C9 comprises Isosorbide-5-Nitrae-heptadiene, 1-heptene, 3,6-nonadienes, 3-nonene, Isosorbide-5-Nitrae, 7-sarohornene.Other possible low molecular weight olefins comprise vinylbenzene and vinyl cyclohexane.In some embodiments, preferably use alkene mixture, described mixture is included in straight chain within the scope of C4-C10 and branched chain low molecular weight alkene.In one embodiment, the mixture (that is, the combination of 1-butylene, 2-butylene and/or iso-butylene) of straight chain and side chain C4 alkene can preferably be used.In other embodiments, the higher range of C11-C14 can be used.
As used in this article, term " middle-molecular-weihydroxyethyl alkene " can refer to any one or combination of undersaturated straight chain, side chain or cyclic hydrocarbon within the scope of C15-C24.Middle-molecular-weihydroxyethyl alkene comprises " alpha-olefin " or " terminal olefine ", and wherein unsaturated C-C is present in an end of compound.Middle-molecular-weihydroxyethyl alkene also can comprise diene or triolefin.Middle-molecular-weihydroxyethyl alkene also can comprise internal olefin or " middle-molecular-weihydroxyethyl internal olefin ".In some embodiments, preferably alkene mixture is used.
As used in this article, term " paraffinic hydrocarbons " can refer to only have single C-C, have general formula C nh 2n+2hydrocarbon compound, wherein, in some embodiments, n is less than about 20.
As used in this article, term " isomerization " can refer to that linear hydrocarbon compounds (such as n-paraffin) is to the reaction of branched hydrocarbon compound (such as isoparaffin) and conversion.In other embodiments, the isomerization of alkene or unsaturated ester represents that carbon-to-carbon double bond transfers to another position in molecule (such as, 8-decylenic acid is changed into) from 9-decylenic acid, or it represents the change (such as, cis to trans) of compound at the geometry at carbon-to-carbon double bond place.As limiting examples, Skellysolve A can be isomerizated into the mixture of Skellysolve A, 2-methylbutane and 2,2-dimethylpropane.The isomerization of n-paraffin can be used for the gross properties improving fuel composition.In addition, isomerization can refer to branched-chain alkane to further, the conversion of the more paraffinic hydrocarbons of higly branched chain.
As used in this article, term " output " can refer to the gross weight of the product obtained by metathesis and hydrogenation.It also can refer to the gross weight of the after product in separating step and/or isomerization reaction.It can define according to output %, wherein by the gross weight of produced product divided by natural oil raw material (with in some embodiments, the low molecular weight olefins of combination and/or middle-molecular-weihydroxyethyl alkene) gross weight.
As used in this article, term " fuel " and " fuel composition " refer to the material or following blend component that meet required specification, described blend component can be used for preparation of fuels composition, but their satisfied necessary specifications for fuel itself is whole.
As used in this article, term " carbon number distribution " can refer to the scope of compound existing in composition, and wherein often kind of compound is defined by the number of existing carbon atom.As limiting examples, naphtha type rocket engine fuel typically comprises such hydrocarbon compound distribution: wherein the major part of those compounds has 5-15 carbon atom separately.Kerosene type jet fuel typically comprises such hydrocarbon compound distribution: wherein the major part of those compounds has 8-16 carbon atom separately.Diesel oil fuel typically comprises such hydrocarbon compound distribution: wherein the major part of those compounds has 8-25 carbon atom separately.
As used in this article, term " diene selective hydration " or " selective hydration " can refer to that many unsaturated olefins and/or ester transform to the target (targeted) of cholesterol alkene and/or ester.A limiting examples comprises the selective hydration of 3,6-12 carbon diene to the cholesterol product such as mixture of 1-dodecylene, 2-dodecylene, 3-dodecylene, 4-dodecylene, 5-dodecylene and/or 6-dodecylene.
As used in this article, term " transformation efficiency " can refer to from many unsaturated olefins and/or ester to the transformation efficiency of saturated ester, paraffinic hydrocarbons, cholesterol alkene and/or cholesterol ester.In other words, the total many unsaturatess in transformation efficiency=(the total many unsaturatess in the total many Bu saturated Wu – product in raw material)/raw material.
As used herein, term " selectivity " can refer to the distribution compared to paraffinic hydrocarbons and/or saturated ester of the cholesterol thing that formed in step of hydrogenation.In other words, total cholesterol thing/(the total saturates in the total cholesterol thing+product in product) in selectivity=product.
As mentioned above, except other valuable components, terminal olefine and internal olefin can derive from natural oil raw material.Can under the existence of metathesis catalyst, by the self-metathesis reaction of natural oil raw material or the cross-metathesis of natural oil raw material and low molecular weight olefins or middle-molecular-weihydroxyethyl alkene using a large amount of valuable component as target.Valuable component like this can comprise fuel composition, sanitising agent, tensio-active agent and other specialty chemicals.The limiting examples of fuel composition comprises jet, kerosene and diesel oil fuel.In addition, also can using ester exchange offspring (that is, the product formed by the transesterify of ester in the presence of an alcohol) as target, its limiting examples comprises: fatty acid methyl ester; Biofuel; 9-decylenic acid (" 9DA ") ester, 9-undecylenic acid (" 9UDA ") ester and/or 9-dodecenoic acid (" 9DDA ") ester; 9DA, 9UDA and/or 9DDA; An alkali metal salt of 9DA, 9UDA and/or 9DDA and alkaline earth salt; The dimer of ester exchange offspring; And composition thereof.
In some embodiments, before replacement(metathesis)reaction, natural oil raw material can be treated to make natural oil be more suitable for follow-up replacement(metathesis)reaction.In some embodiments, natural oil is preferably vegetables oil or vegetable oil derivatives, such as soybean oil.
In one embodiment, natural oil handling relates to removing catalyzer poison such as superoxide, and described catalyzer poison can reduce the activity of metathesis catalyst potentially.The limiting examples of natural oil material processing reducing catalyzer poison comprises and is described in PCT/US2008/09604, PCT/US2008/09635 and U.S. Patent Application No. 12/672,651 and 12/672, those in 652, its full content is incorporated herein by reference.In some embodiments, natural oil raw material is by heat-treating as follows: be heated to when there is not oxygen (oxygen) by raw material be greater than 100 DEG C of temperature and keep being enough to time of the catalyzer poison reduced in raw material at such a temperature.In other embodiments, temperature is about 100 DEG C-300 DEG C, about 120 DEG C-250 DEG C, about 150 DEG C-210 DEG C or about 190-200 DEG C.In one embodiment, by realizing not existing of oxygen with nitrogen to natural oil raw material bubbling (injection), wherein nitrogen pumps in Feedstock treating container with the pressure of about 10atm (150psig).
In some embodiments, natural oil raw material carries out chemical treatment by the chemical reaction of catalyzer poison under the condition being enough to the catalyzer poison reduced in raw material.In some embodiments, raw material reductive agent or positively charged ion-mineral alkali compositions-treated.The limiting examples of reductive agent comprises hydrosulphite, hydroborate, phosphine, thiosulphate, combines individually or with it.
In some embodiments, natural oil raw material sorbent treatment is to remove catalyzer poison.In one embodiment, the combined treatment of raw material heat and adsorbent method.In another embodiment, the combined treatment of raw material chemistry and adsorbent method.In another embodiment, process relates to the hydrogen treatment of part to change the reactivity of natural oil raw material and metathesis catalyst.When discussing various metathesis catalyst, hereafter also illustrate the other limiting examples of Feedstock treating.
In some embodiments, natural oil raw material the first reagent (means), the second reagent, the 3rd reagent and/or any extra agent treated are to remove catalyzer poison.First, second, third and/or any extra reagent can be selected from heating, molecular sieve, aluminum oxide (aluminum oxide), silica gel, illiteracy unsticking soil, Fuller's earth, bleaching clay, diatomite individually (such as, with trade(brand)name CELITE sell), zeolite, kaolin, activated metal (such as, Cu, Mg etc.), acid anhydrides (such as, diacetyl oxide " Ac 2o " etc.), gac (also referred to as activated charcoal), SODA ASH LIGHT 99.2, metal hydride (such as, alkaline earth metal hydride such as CaH 2deng), metal sulfate (such as, alkaline earth metal sulphate such as calcium sulfate, magnesium sulfate etc.; Alkali metal sulfates is potassium sulfate, sodium sulfate etc. such as; With other metal sulfates such as Tai-Ace S 150, potassium magnesium sulfate etc.), metal halide (such as, alkaline earth metal halide such as Repone K etc.), metal carbonate (such as, calcium carbonate, sodium carbonate etc.), metal silicate (such as, Magnesium Silicate q-agent etc.), Vanadium Pentoxide in FLAKES, metal alanates (such as, composite alkali aluminum hydride such as LiAlH 4, NaAlH 4deng), alkyl aluminum hydride (such as, iBu 2alH, also referred to as DIBALH), metal borohydride (such as, alkali metal borohydride such as LiBH 4, NaBH 4deng), metal alkoxide, organometallic reagent (such as, Grignard reagent; Organolithium reagent is n-Butyl Lithium, tert-butyl lithium, s-butyl lithium such as; Trialkylaluminium is triethyl aluminum (" Et such as 3al "), tri-butyl aluminum, triisopropylaluminiuand, trioctylaluminum (" Oc 3al ") etc., metal amide (acid amides) (such as, lithium diisopropylamine (also referred to as LDA), two (trimethyl silyl) aminocompound (acid amides) the such as KHMDS of metal etc.), carbon carries palladium (Pd/C) catalyzer and combination thereof.
In some embodiments, the first reagent of use is instructed according to the present invention, second reagent, 3rd reagent and/or any extra reagent are selected from heating separately individually, optionally (non-essential) heat treated molecular sieve, optionally heat treated aluminum oxide (such as, active, acid, alkalescence with neutrality), optionally heat treated silica gel, illiteracy unsticking soil, Fuller's earth, bleaching clay, diatomite (such as, sell with trade(brand)name CELITE), zeolite, kaolin, activated metal, acid anhydrides, gac, SODA ASH LIGHT 99.2, metal hydride, metal sulfate, metal halide, metal carbonate, metal silicate, Vanadium Pentoxide in FLAKES, metal alanates, alkyl aluminum hydride, metal borohydride, metal alkoxide, organometallic reagent, metal amide etc., and combination.
In some embodiments, the first reagent of use is instructed according to the present invention, second reagent, 3rd reagent and/or any extra reagent are selected from optionally heat treated activated molecular sieve separately individually, optionally heat treated activated alumina, optionally heat treated active acidic aluminum oxide, optionally heat treated active neutral aluminum oxide, optionally heat treated activated basic alumina, alkaline earth metal hydride, alkaline earth metal sulphate, alkali metal sulfates, alkaline earth metal halide, composite alkali aluminum hydride, alkali metal borohydride, aluminium-alcohol salt, Titanium alkoxides, zirconium alkoxide, cupric alkoxide, ferrite, cerium alkoxide, silicon alkoxide, Grignard reagent, two (trimethyl silyl) aminocompounds of organolithium reagent, trialkylaluminium, metal etc. and combination thereof.
In some embodiments, the first reagent of use, the second reagent, the 3rd reagent and/or any extra reagent is instructed to be selected from CaH individually separately according to the present invention 2, activation Cu, activation Mg, diacetyl oxide, calcium sulfate, magnesium sulfate, potassium sulfate, Tai-Ace S 150, potassium magnesium sulfate, sodium sulfate, calcium carbonate, sodium carbonate, Magnesium Silicate q-agent, Repone K, Li-Al hydrogen compound, sodium alanate, triisobutyl alanate, metal methoxide salt, metal ethoxides, metal n-propyl alcohol salt, metal isopropoxide, metal butanolate, metal 2-methyl-prop alkoxide, metal tert butoxide, titanium isopropylate, aluminum ethylate, aluminum isopropylate, ethanol zirconium, and combination, n-Butyl Lithium, tert-butyl lithium, s-butyl lithium, triethyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, trioctylaluminum, lithium diisopropylamine, potassium hexamethyldisilazide (KHMDS) etc., and combination.
In some embodiments, the first reagent of use, the second reagent, the 3rd reagent and/or any extra reagent is instructed to be connected to solid carrier individually and optionally separately according to the present invention.The representational solid carrier of use is instructed to comprise according to the present invention, but be not limited to, carbon, silicon-dioxide, silica-alumina, aluminum oxide, clay, Magnesium Silicate q-agent (such as, Magnesols), the synthetic silica sorbent material sold with trade(brand)name TRISYL by W.R.Grace & Co., diatomite, polystyrene, macropore (MP) resin etc. and combination thereof.
Typically, there are some selections of different and often complementary reagent, from wherein carrying out selecting with at the contaminated raw material of the pre-treatment of replacement(metathesis)reaction during preparation.Although be undesirably bound to any particular theory and be not intended to the scope with any measure restriction claims or its equivalent, but think at present, non exhaustive and the non-limiting list of following representative treatment process can be used for processing raw material containing regulation pollutent (condition be any functional group on reagent and raw material and/or compatible with pollutent itself etc.): (a) thermal treatment-such as heat (and/or distillation) raw material (such as, about 100 DEG C of-Yue 250 DEG C, or about 200 DEG C in some embodiments-depend on the boiling point of raw material, optionally with rare gas element such as N 2and/or analogue purges) and/or can be used for decompose hydroperoxide pollutent and/or its degradation production with sorbent material (such as, aluminum oxide etc.) process, b () uses acid anhydrides (such as, diacetyl oxide, Ac 2o) process can be used for removing moisture, active hydroxyl material (such as, alcohol) and hydroperoxide (passing through acetylize), c () uses siccative (such as, silica gel, aluminum oxide, molecular sieve, magnesium sulfate, calcium sulfate etc. and combination thereof) and/or organometallic reagent is (such as, tert-butyl lithium, triethyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, trioctylaluminum etc. and combination thereof) and/or metal hydride (such as, CaH 2deng) and/or acid anhydrides (such as, diacetyl oxide etc.) process can be used for remove moisture, d () uses sorbent material (such as, aluminum oxide, silica gel etc. and combination thereof) and/or organometallic reagent is (such as, tert-butyl lithium, triethyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, trioctylaluminum etc. and combination thereof) and/or metal amide (such as, LDA, KHMDA etc.) process can be used for except deprotonation material, e () can be used for removing polar material with sorbent material (such as, aluminum oxide, silica gel, activated charcoal etc. and combination thereof) process, f () can be used for removing lewis base property catalyzer poison etc. with organometallic reagent (such as, tert-butyl lithium, triethyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, trioctylaluminum etc. and combination thereof) process.
In some embodiments, the first reagent for the pre-treatment raw material in replacement(metathesis)reaction comprises sorbent material, in some embodiments, it is selected from silica gel, aluminum oxide, bleaching clay, gac, molecular sieve, zeolite, Fuller's earth, diatomite etc. and combination thereof.In some embodiments, the first reagent is selected from optionally heat treated molecular sieve, optionally heat treated aluminum oxide and combination thereof.In some embodiments, sorbent material comprises optionally heat treated activated alumina, in some embodiments, it is selected from optionally heat treated active acidic aluminum oxide, optionally heat treated active neutral aluminum oxide, optionally heat treated activated basic alumina and combination thereof.In some embodiments, sorbent material comprises optionally heat treated active neutral aluminum oxide, and it can be used for processing for acid catalyzed isomerization and/or resets responsive raw material (such as, alkene).
For wherein instructing the first reagent of use, the second reagent, the 3rd reagent and/or any extra reagent to comprise sorbent material (such as according to the present invention, molecular sieve, aluminum oxide etc.) embodiment, think at present, compare at the raw material of container bottom with sorbent material is joined simply, more effectively carry out by using diafiltration or flow model system (such as, chromatographic column) to make raw material flow through the first reagent with sorbent treatment raw material.In some embodiments, in post, use the aluminum oxide of about 20 % by weight.Although be undesirably bound to any particular theory and be not intended to the scope with any measure restriction claims or its equivalent, think at present, raw material alumina treatment is effective for some embodiments by about 5:1 weight ratio basis.But understand, the amount of the aluminum oxide used does not limit, and beyond the impact of oxidated aluminium form, its activation method and clear and definite treatment process (such as, flowing through post relative to directly joining in container), also depend on both raw material and impurity.
In some embodiments, trialkylaluminium is comprised for the first reagent of the pre-treatment raw material in replacement(metathesis)reaction, the second reagent, the 3rd reagent and/or any extra reagent, in some embodiments, it is selected from triethyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, trioctylaluminum, triisobutyl aluminium etc. and combination thereof.Although be undesirably bound to any particular theory and be not intended to the scope with any measure restriction claims or its equivalent, but think at present, in some cases, under the metathesis catalyst of lower concentration, greatly feed stock conversion is improved with trialkylaluminium process raw material, but under the existence of excessive trialkylaluminium, catalyst performance affects adversely.Therefore, (such as, use trialkylaluminium as the first reagent and/or when using excessive trialkylaluminium) in some embodiments, can comprise sorbent material for the treatment of the reagent in succession of raw material, it can remove excessive trialkylaluminium.In other embodiments, for the treatment of the amount of the trialkylaluminium of raw material by following minimizing: first use described dissimilar reagent herein (such as, sorbent material, include but not limited to molecular sieve, aluminum oxide and/or analogue) process raw material, then introduce trialkylaluminium as second (or follow-up) reagent to remove residual contaminants.Under any circumstance, although be undesirably bound to any particular theory and be not intended to the scope with any measure restriction claims or its equivalent, but think at present, remove excessive trialkylaluminium from organic product should carry out very modestly, the sorbent material due to mistake in can cause highly exothermic reactions or highly unstable material.In some embodiments, trialkylaluminium is attached on solid carrier and removes to simplify it.
In some embodiments, molecular sieve can be used as the first reagent with a large amount of (in bulk, overall) dried feed, then " height heat treated " aluminum oxide can be used as the second reagent to remove extra moisture, and last molecular sieve can be used as the 3rd reagent finally with removing still further residual moisture.In other embodiments, molecular sieve can be used as the first reagent with a large amount of (in bulk, overall) dried feed, then " height heat treated " aluminum oxide can be used as the second reagent to remove extra moisture, and last trialkylaluminium (such as, triethyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, trioctylaluminum, triisobutyl aluminium etc. and combination thereof) can be used as the 3rd reagent to remove any moisture residual further.
In an embodiment, activated copper powder uses individually or with other treatment combination.Such as, in some embodiments, activated copper powder uses with heat (such as, under a nitrogen 200 DEG C at least 2 hours), molecular sieve and/or trialkylaluminium treatment combination.In another embodiment, activate magnesium chips (tunings) to use individually or with other treatment combination.Such as, in some embodiments, activate magnesium chips to use with heat (such as, under a nitrogen 200 DEG C at least 2 hours), molecular sieve and/or trialkylaluminium treatment combination.
In another embodiment, diacetyl oxide uses individually or with other process/agent combination.Such as, in some embodiments, diacetyl oxide and aluminum oxide (aluminum oxide) and/or trialkylaluminium treatment combination use.In other embodiments, diacetyl oxide and aluminum oxide, distillation, molecular sieve and/or trialkylaluminium treatment combination use.In addition, the diafiltration on activated alumina or molecular sieve can be applied or can be used for alternative trialkylaluminium process before trialkylaluminium process.
In another embodiment, aluminum oxide uses individually or with other process/agent combination.In one embodiment, aluminum oxide and carbon carry palladium (Pd/C) catalyzer and/or trialkylaluminium treatment combination uses.
In addition, in some embodiments, low molecular weight olefins or middle-molecular-weihydroxyethyl alkene also can in the pre-treatments of the replacement(metathesis)reaction with natural oil.As natural oil process, any above-mentioned disposal methods low molecular weight olefins or middle-molecular-weihydroxyethyl alkene can be used can to affect or reduce the poisonous substance of catalyst activity with removing.
In some embodiments, low molecular weight olefins or middle-molecular-weihydroxyethyl alkene can self-metathesis to form metathetic low molecular weight olefins or metathetic middle-molecular-weihydroxyethyl alkene, with regulate the character of alkene and with the metathesis of natural oil after potential product.In some embodiments, low molecular weight olefins or middle-molecular-weihydroxyethyl alkene are at rhenium oxide catalysts (such as, be carried on the rhenium oxide on aluminum oxide) or tungsten oxide catalyst (such as, being carried on the Tungsten oxide 99.999 on silicon-dioxide) existence under self-metathesis.This reaction can be carried out in fixed-bed reactor.In one embodiment, low molecular weight olefins is 1-butylene.Low molecular weight olefins can in fixed-bed reactor on rhenium oxide catalysts self-metathesis mainly to produce 3-hexene and ethene.Ethene can be separated for process further (processing, processing) from reactor effluent, such as delivers to ethylene purification system or ethylene oxide system.Unreacted low molecular weight olefins (such as, 1-butylene) can be recycled to fixed-bed reactor and metathetic low molecular weight olefins (such as, 3-hexene) can be delivered to double decomposition reactor for the metathesis with natural oil.
In other embodiments, with the metathesis of natural oil before by low molecular weight olefins or middle-molecular-weihydroxyethyl isomerisation of olefin.By isomerization regulate the composition of low molecular weight olefins or middle-molecular-weihydroxyethyl alkene and character can allow low molecular weight olefins or middle-molecular-weihydroxyethyl alkene from form different product or different proportion of products after natural oil metathesis.In some embodiments, isomerization or branched chain low molecular weight alkene are within the scope of C4-C10.In one embodiment, hexene isomerization is to form branched chain low molecular weight alkene.The limiting examples of branched chain low molecular weight alkene comprises iso-butylene, 3-methyl-1-butene, 2-methyl-3-amylene and 2,2-dimethyl-3-amylene.
By using branched chain low molecular weight alkene or side chain middle-molecular-weihydroxyethyl alkene in replacement(metathesis)reaction, metathesis product will comprise branched-chain alkene, and it can be hydrogenated to isoparaffin subsequently.In some embodiments, branched chain low molecular weight alkene or side chain middle-molecular-weihydroxyethyl alkene can help to realize fuel composition such as jet, kerosene or the performance needed for diesel oil fuel.In some embodiments, by the isomerization of low molecular weight olefins after metathesis and separating step using C11-C14 alkene as target.In other embodiments, branched chain low molecular weight alkene or side chain middle-molecular-weihydroxyethyl alkene can be used as the helpful as target compared with the ester of long-chain of sanitising agent or cleaning compositions.In some embodiments, can after metathesis, separation and step of transesterification (hereafter discussing in detail) using C10-C15 or C11-C14 methyl esters as target.Isomerization reaction is well known in the art, as U.S. Patent number 3, and 150,205; 4,210,771; 5,095,169; With 6,214, described in 764, its full content is incorporated herein by reference.
As shown in fig. 1, after this optional process of natural oil raw material, low molecular weight olefins and/or middle-molecular-weihydroxyethyl alkene, natural oil 12 is with self or react under the existence of metathesis catalyst in double decomposition reactor 20 in combination with low molecular weight olefins 14 or middle-molecular-weihydroxyethyl alkene 15.Hereafter discuss metathesis catalyst and metathesis reaction conditions in more detail.In some embodiments, under the existence of metathesis catalyst, natural oil 12 stands to react with the self-metathesis of self.In other embodiments, under the existence of metathesis catalyst, natural oil 12 stands the cross-metathesis with low molecular weight olefins 14 or middle-molecular-weihydroxyethyl alkene 15.In some embodiments, natural oil 12 stands self and both cross-metathesis in parallel double decomposition reactor.Self-metathesis and/or cross-metathesis form metathesis product 22, and wherein metathesis product 22 comprises alkene 32 and ester 34.
In some embodiments, low molecular weight olefins 14 is in the scope of C2-C6.As limiting examples, in one embodiment, low molecular weight olefins 14 can comprise following at least one: ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 3-amylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentenes, Isosorbide-5-Nitrae-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-amylene, 3-methyl-2-amylene, 4-methyl-2-amylene, 2-methyl-3-amylene and tetrahydrobenzene.The limiting examples of the low molecular weight olefins within the scope of C7-C9 comprises Isosorbide-5-Nitrae-heptadiene, 1-heptene, 3,6-nonadienes, 3-nonene, Isosorbide-5-Nitrae, 7-sarohornene.In another embodiment, low molecular weight olefins 14 comprises at least one of vinylbenzene and vinyl cyclohexane.In another embodiment, low molecular weight olefins 14 can comprise at least one of ethene, propylene, 1-butylene, 2-butylene and iso-butylene.In another embodiment, low molecular weight olefins 14 comprises the alpha-olefin of at least one within the scope of C2-C10 or terminal olefine.
In another embodiment, low molecular weight olefins 14 comprises the branched chain low molecular weight alkene of at least one within the scope of C4-C10.The limiting examples of branched chain low molecular weight alkene comprises iso-butylene, 3-methyl-1-butene, 2-methyl-3-amylene and 2,2-dimethyl-3-amylene.
In some embodiments, middle-molecular-weihydroxyethyl alkene 15 is included in undersaturated straight chain, side chain or the cyclic hydrocarbon within the scope of C15-C24.In some embodiments, middle-molecular-weihydroxyethyl alkene is alpha-olefin or terminal olefine.
As mentioned above, the mixture of various straight or branched low molecular weight olefins and straight or branched middle-molecular-weihydroxyethyl alkene can be used in the reaction to realize required metathesis product distribution.In some embodiments, mixture comprises straight chain and/or branched chain low molecular weight alkene.In other embodiments, mixture comprises straight chain and/or side chain middle-molecular-weihydroxyethyl alkene.In one embodiment, the mixture of butylene (1-butylene, 2-butylene and optionally iso-butylene) can be used as low molecular weight olefins, and it provides low cost, commercially available raw material, instead of a kind of purified source of specific butylene.The mixed butenes feedstock of such low cost is typically diluted with normal butane and/or Trimethylmethane.
In some embodiments, except natural oil 12 and low molecular weight olefins in some embodiments 14 and/or middle-molecular-weihydroxyethyl alkene 15, the recirculation stream from downstream separation unit can be introduced in double decomposition reactor 20.Such as, in some embodiments, double decomposition reactor can be back to from the C3-C4 bottoms of overhead product (overhead) separating unit and/or C2-C6 recirculation olefin stream.In one embodiment, as shown in fig. 1, the light olefin stream 44 from separation of olefins unit 40 can be back to double decomposition reactor 20.In another embodiment, C3-C4 bottoms and light olefin stream 44 combined and be back to double decomposition reactor 20.In another embodiment, the C15+ bottoms 46 from separation of olefins unit 40 is back to double decomposition reactor 20.In another embodiment, all aforementioned recirculation stream are back to double decomposition reactor 20.In another embodiment, recirculation stream one or more optionally hydrogenation to increase the concentration of monoolefine in logistics.
In other embodiments, the various ester logistics in transesterify unit (hereafter discuss) downstream also can recirculation or be back to double decomposition reactor 20.In some embodiments, glycerolysis reaction can be carried out to prevent free glycerol from entering double decomposition reactor 20 or to limit its amount to the logistics of recirculation ester.In some embodiments, the logistics of recirculation ester stands purification step is recycled to the methyl alcohol of double decomposition reactor 20 amount with restriction.In some embodiments, before carrying out glycerolysis reaction and entering double decomposition reactor 20, the logistics of recirculation ester and low molecular weight olefins 14 and/or middle-molecular-weihydroxyethyl alkene 15 are merged.In another embodiment, the logistics of recirculation ester can part or optionally hydrogenation to increase the concentration of cholesterol ester in logistics.Glycerolysis reaction also can limit or prevent free fatty acid methyl esters from entering replacement(metathesis)reaction and subsequently as leaving double decomposition reactor in the form of the free fatty acid methyl esters close to the boiling of various high value olefin product places.Under these circumstances, between alkene with ester separation period, these methyl esters components can be separated together with alkene.Such methyl esters component can be difficult to by distillation and separation of olefins.
Replacement(metathesis)reaction in double decomposition reactor 20 produces metathesis product 22.In one embodiment, metathesis product 22 enters flasher, and this flasher is causing C2 or C2-C3 compound to flash off and operating under the temperature and pressure condition of tower top removing.C2 or C2-C3 lighting end (lightend) major part is made up of the hydrocarbon compound with carbon number 2 or 3.In some embodiments, then overhead product separating unit is delivered in C2 or C2-C3 lighting end, wherein C2 or C2-C3 compound is further in tower top and the compound separation compared with heavy flashed off together with C2-C3 compound.These typically are the C3-C5 compound carried by C2 or C2-C3 compound at tower top compared with the compound of heavy.After being separated in overhead product separating unit, then tower top C2 or C2-C3 logistics can be used as fuel source.These hydrocarbon have in fuel composition himself value extraneous, and can use in this stage or be separated for other valuable composition and application.In some embodiments, the main bottoms containing C3-C5 compound from overhead product separating unit is back to double decomposition reactor as recirculation stream.In flasher, the metathesis product 22 not in flash overhead is delivered to downstream to be separated in separating unit 30 such as distillation tower.
Before separating unit 30, in some embodiments, metathesis product 22 can with for deactivate or the reactant of extracting catalyst or reagent contact.In some embodiments, metathesis product 22 is introduced sorbent material or complexing agent to promote being separated of metathesis product 22 and metathesis catalyst.In one embodiment, sorbent material or complexing agent are clay bed.Clay bed will adsorb metathesis catalyst, and after filtration step, metathesis product 22 can be delivered to separating unit 30 and be used for further process.In another embodiment, sorbent material or complexing agent are water-soluble phosphine reagent such as tris(hydroxymethyl)phosphine (THMP).By going out (pouring out gently, decanting) aqueous phase from organic phase decant, catalyzer is separated by known liquid-liquid extraction mechanism with water-soluble phosphine.
In some embodiments, metathesis product 22 can be delivered to catalyst kill tank (drum), wherein add described reagent (such as, the THMP aqueous solution) to deactivate metathesis catalyst.Relative to the catalyzer pumping into catalyst kill tank, the speed that can be equivalent at least 1:1,5:1,10:1,25:1 or 50:1 mol ratio adds THMP.
In some embodiments, described reagent (such as, THMP) can be stayed in metathesis product 22 and to bring into together whole or in part in follow-up chemical reaction or treatment step.In other embodiments, before any subsequent reactions or treatment step, can be separated partially or completely from mixture and remove described reagent.In some embodiments, passivation and extraction can be attached to (such as, by providing described reagent in extract wood material) in a step.
In one embodiment, there is catalyst separating by effluent is delivered to catalyzer decanting vessel tank from catalyst kill tank.Decanting vessel tank can be used as the horizontal vessel with vertical baffle and protective guard (susceptor, boot) and works to collect the aqueous phase containing metathesis catalyst.In some embodiments, decanting vessel tank under the pressure of the temperature of about 60-90 DEG C and 1-1.5atm, or operates under about 53 DEG C (127 °F) and 1.1atm (16psia).
In other embodiments, catalyst separating comprises with polar solvent washing or extraction mixture (such as, especially, although not exclusively, wherein said reagent being dissolved at least in part to the embodiment in polar solvent).In some embodiments, after catalyzer deactivation, polar solvent is added in subsequent steps.In other embodiments, polar solvent (such as water) is approximately being added metathesis product 22 with deactivation reagent (such as, THMP) simultaneously.Deactivation reagent and polar solvent are almost added metathesis product simultaneously and can eliminate needs for extra reaction/separation container, this can Simplified flowsheet and save capital potentially.
In some embodiments, polar solvent and mixture unmixing at least in part, making can the separation of genetic horizon.In some embodiments, described reagent is at least partially dispensed in polar solvent, layer, and then it can be separated from immiscible rest layers and remove.The representational polar solvent of use is instructed to comprise according to the present invention, but be not limited to, water, alcohol (such as, methyl alcohol, ethanol etc.), ethylene glycol, glycerine, DMF, multifunctional polar compound (including but not limited to polyoxyethylene glycol and/or glyme), ionic liquid etc. and combination thereof.In some embodiments, mixture is extracted with water.In some embodiments, when hydrolyzable phosphorous acid ester at least in part (such as, in some embodiments, there is low-molecular-weight phosphorous acid ester, include but not limited to trimethyl phosphite, triethyl-phosphite and combination thereof) as reagent time, wash mixture with water and phosphorous acid ester can be changed into corresponding acid.Although be undesirably bound to any particular theory and be not intended to the scope with any measure restriction claims or its equivalent, think at present, adopt the ester of lower molecular weight such hydrolysis can occur more quickly.
In some embodiments, when with polar solvent extract being expectation, extraction can comprise high shear mixing (such as, be enough to first-phase and/or chemical substance are disperseed and/or be delivered to the mixing of the type in second-phase at least partially, described first-phase and/or chemical substance usually with described second-phase unmixing at least in part), although mixing so in some embodiments can contribute to forming less desirable emulsion.In some embodiments, extraction comprises low strength mixing (such as, the stirring of non-high-shear).The present invention's instruction is limited to any particular type or the time length of mixing never in any form.But, for purposes of illustration, in some embodiments, extraction comprises polar solvent and mixture to mix and reaches at least about 1 second, 10 seconds, 30 seconds, 1 minute, 2 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes.Although be undesirably bound to any particular theory and be not intended to the scope with any measure restriction claims or its equivalent, but think at present, when an online (column, inline) when shear-mixed is for mixing, shorter mixing time (such as, on the order of a second) is attainable.
When with polar solvent extract be expect time, the present invention's instruction is limited to never in any form and adds any specified quantitative of polar solvent of mixture for extracting.But, for purposes of illustration, in some embodiments, add mixture is greater than mixture weight for the amount by weight of the polar solvent (such as, water) extracted.In some embodiments, mixture is less than mixture weight for the amount by weight of the polar solvent (such as, water) extracted is added.In some embodiments, mixture is at least about 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1,20:1,40:1 or 100:1 with the weight ratio of the water adding mixture.For higher oil to water ratio, the extraction and fractionation of whizzer and/or coalescer is used to can be expectation.
In some embodiments, when with polar solvent extract being expectation, that instructs according to the present invention allows sedimentation to be separated with promotion period for suppressing the method for dehydrogenation to be included in further after polar solvent washs.The present invention's instruction is limited to any specific time length in sedimentation period never in any form.But for purposes of illustration, in some embodiments, sedimentation is at least about 1 minute period, 2 minutes, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 60 minutes or 120 minutes.
Remove with polar solvent purging compound to remove described reagent (such as, THMP) beyond or alternatively scheme-optionally comprise by being adsorbed on sorbent material and being removed by described reagent at least partially further according to the method for the present invention's instruction, then described sorbent material is optionally from mixture physical sepn (such as, by filtering, centrifugal, crystallization etc.).In some embodiments, sorbent material is polarity.The representative sorbent material of use is instructed to comprise according to the present invention, but be not limited to, carbon, silicon-dioxide, silica-alumina, aluminum oxide, clay, Magnesium Silicate q-agent (such as, Magnesols), the synthetic silica sorbent material sold with trade(brand)name TRISYL by W.R.Grace & Co., diatomite, polystyrene, macropore (MP) resin etc. and combination thereof.
In addition, in some embodiments, before separating unit 30 (and in some cases after catalyst separating), metathesis product 22 can be delivered to hydrogenation unit, the carbon-to-carbon double bond hydrogen portion ground wherein in alkene and ester, optionally or fully saturated.Hydrogenation can be carried out for any currently known methods of the double bond containing the compound such as alkene and ester that exist in hydrogenation metathesis product 22 according in this area.In some embodiments, metathesis product partly or optionally hydrogenation to increase the concentration of cholesterol alkene and/or the ester cpds existed in metathesis product 22.In some embodiments, in diene selective hydration, can be at least 50%, at least 75%, at least 85%, at least 95% or at least 98% from many unsaturated olefins and ester to the transformation efficiency of paraffinic hydrocarbons, saturated ester, cholesterol alkene and cholesterol ester.Selectivity to cholesterol alkene and cholesterol ester instead of paraffinic hydrocarbons and saturated ester is at least 90%, at least 95%, at least 99% or at least 99.5%.
In some embodiments, in hydrogenation unit, hydrogen and metathesis product 22 are reacted in the presence of a hydrogenation catalyst to produce and are comprised part to the paraffin/olefin of fully hydrogenation and part to the hydrogenated products of the ester of fully hydrogenation.
In some embodiments, by metathesis product 22 hydrogenation under the existence of hydrogenation catalyst comprising nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium or iridium (combining individually or with it).Useful catalyzer can be heterogeneous or homogeneous phase.In some embodiments, catalyzer is nickel or the sponge ni-type catalyzer of load.
In some embodiments, hydrogenation catalyst comprises the nickel (that is, reduced nickel) being reduced into activated state with hydrogen chemistry be provided on carrier.Carrier can comprise porous silicon (such as, diatomite (kieselguhr, infusorial, diatomaceous or siliceousearth)) or aluminum oxide.The feature of catalyzer is high nickel surface area/gram nickel.The commercial embodiments of the Ni hydrogenation catalysts of load comprise with trade names " NYSOFACT ", " NYSOSEL " and " NI5248D " (from BASFCatalystsLLC, Iselin, NJ) obtainable those.The Ni hydrogenation catalysts of other load comprises with trade names " PRICAT9908 ", " PRICAT9910 ", " PRICAT9920 ", " PRICAT9932 ", " PRICAT9936 ", " PRICAT9939 ", " PRICAT9953 ", " PRICAT20/15D ", " PRICATNI52/35P ", " PRICATNI55/5P ", " PRICATNI60/15P ", " PRICATNI62/15P ", " PRICATNI52/35T ", " PRICATNI55/5T " and " PRICATNI60/15T " (can available from JohnsonMattheyCatalysts, WardHill, MA) (wherein D=droplet, P=powder, and T=sheet) commercially available those.The nickel catalyzator of load can be U.S. Patent number 3,351,566, U.S. Patent number 6,846,772, the type that describes in EP0168091 and EP0167201, its full content is incorporated herein by reference.
In other embodiments, hydrogenation catalyst comprises the copper (that is, going back native copper) being reduced into activated state with hydrogen chemistry be provided on carrier.Carrier can comprise porous silicon (such as, diatomite (kieselguhr, infusorial, diatomaceous or siliceousearth)) or aluminum oxide.The copper hydrogenation catalyst of load commercial embodiments comprises " PRICATCU60/8T ", " PRICATCU60/35T ", " PRICATCU50/8P " and " PRICATCU60/35P " (can available from JohnsonMattheyCatalysts, WardHill, MA) (wherein T=sheet and P=powder).
Hydrogenation can batchwise process or carry out with successive processes and can be part, selectivity or completely hydrogenation.In some embodiments, hydrogenation is selective hydration, many unsaturated olefins wherein in metathesis product 22 or ester are optionally saturated has the cholesterol alkene of more a large amount or the composition of ester, the complete stable hydrocarbon generated with limit or the amount of saturated ester to be formed.In some embodiments, part or selective hydrogenation can 10-360 minute, time period of 20-240 minute, 30-180 minute or 60-90 minute scope carries out.
In some embodiments, the temperature range of part or selective hydration step is about 50 DEG C of-Yue 350 DEG C, about 100 DEG C of-Yue 300 DEG C, about 150 DEG C-Yue 250 DEG C, about 100 DEG C-Yue 150 DEG C, about 150 DEG C or about 180 DEG C.Temperature requiredly can such as to change with hydrogen pressure.Typically, higher gaseous tension needs lower temperature.Hydrogen is pumped in reaction vessel to realize required H 2gaseous tension.In some embodiments, H 2the scope of gaseous tension is about 15psig (1atm)-Yue 3000psig (204.1atm), about 15psig (1atm)-Yue 90psig (6.1atm) or about 50psig (3.4atm)-Yue 500psig (34atm).Along with gaseous tension increases, more special high-pressure treatment apparatus can be needed.In some embodiments, reaction conditions is " gentle ", and wherein temperature is about 50 DEG C of-Yue 100 DEG C and H 2gaseous tension is less than about 100psig.In other embodiments, temperature is about 100 DEG C of-Yue 150 DEG C, and pressure is about 50psig (3.4atm)-Yue 500psig (34atm).In some embodiments, temperature is about 150 DEG C and hydrogen pressure is about 100psig (6.8atm).In other embodiments, temperature is about 180 DEG C and hydrogen pressure is about 100psig (6.8atm).When reaching required degree of hydrogenation, reactive material is cooled to required filtration temperature.
Typically consider the amount of many factors selective hydrogenation catalyzer, described factor comprises, such as, degree of unsaturation in the type of the hydrogenation catalyst used, the amount of raw material used, material to be hydrogenated, required hydrogenation ratio (speed), required degree of hydrogenation (such as, as measured by iodine number (IV)), the selectivity of hydrogenation, the purity of reagent and H 2gaseous tension.In some embodiments, with about 10 % by weight of handled substrate or less, such as about 5 % by weight or less about 1 % by weight or less amount use hydrogenation catalyst.In some embodiments, the amount of hydrogenation catalyst is 0.01-1.0 % by weight, 0.02-0.5 % by weight or the 0.1-0.25 % by weight of handled substrate (such as, metathesis product 22 or alkene 32, as described below).
In some embodiments, the recycling or recirculation of hydrogenation catalyst is used for follow-up use or for repeatedly using.In some embodiments, by hydrogenation catalyst recirculation once.In other embodiments, by its recirculation twice or three times or more.
When reaching required degree of hydrogenation, reactive material is cooled to required filtration temperature.During hydrogenation, by hydrogen, carbon-to-carbon double bond part is extremely completely saturated.In one embodiment, the alkene in metathesis product 22 and hydrogen reaction are to form the fuel composition only comprising or mainly comprise paraffinic hydrocarbons.In addition, the ester from metathesis product is complete or almost entirely saturated in hydrogenation unit.In other embodiments, gained hydrogenated products only comprises the alkene of fractional saturation and the ester of fractional saturation.In some embodiments, the cholesterol alkene that increased by per-cent of gained selective hydration product and/or ester form.
In separating unit 30, in some embodiments, metathesis product 22 (from hydrogenation unit, double decomposition reactor 20 or catalyst separating unit) is separated at least two product stream.In one embodiment, metathesis product 22 is delivered to separating unit 30 or distillation tower, to be separated with ester 34 by alkene 32.In another embodiment, C is comprised 7can remove from separating unit 30 by flow measurement with the by-product stream of cyclohexadiene (such as, 1，4-cyclohexadiene).In some embodiments, the alkene 32 of separation can comprise the hydrocarbon with the carbon number being up to 24.In some embodiments, ester 34 can comprise metathetic glyceryl ester.In other words, preferably tower top be separated or distill comparatively light ends alkene 32 for the treatment of one-tenth compositions of olefines, and by primarily of have carboxylic acids/esters functionality compound composition ester 34 introduce in bottoms.Based on be separated quality (quality), some ester cpds can be brought in overhead product olefin stream 32, and also can by some comparatively heavy olefins bring in ester logistics 34.In addition, the cyclohexadiene (such as, 1，4-cyclohexadiene) of separation can process to form benzene further in dehydrogenation step.The example of catalytic dehydrogenation catalyst comprises the platinum be carried on aluminum oxide.The example of oxy-dehydrogenation catalyst comprises the mixed metal oxide be made up of molybdenum, vanadium, niobium, tellurium, magnesium and/or aluminium.Other dehydrogenation catalyst examples comprise cerium/zirconium, alkaline earth/nickel, calcium-nickel-phosphoric acid salt, chromium, iron-chromated oxide, bismuth/molybdenum, tin/antimony, silver or copper.
In one embodiment, alkene 32 can be collected and sell for a large amount of known application.In other embodiments, process alkene 32 (wherein olefinic bonds hydrogen 48 is saturated, as described below) further in separation of olefins unit 40 and/or hydrogenation unit 50.In other embodiments, alkene 32 optionally hydrogenation to increase mono-olefins concentration.In other embodiments, be used for being further processed as various product as bottoms using comprising being separated compared with heavy ends glyceryl ester with the ester 34 of free fatty acids or distilling.In some embodiments, further process can using the generation of following limiting examples as target: fatty acid methyl ester; Biofuel; 9DA ester, 9UDA ester and/or 9DDA ester; 9DA, 9UDA and/or 9DDA; An alkali metal salt of 9DA, 9UDA and/or 9DDA and alkaline earth salt; The diacid of ester exchange offspring and/or diester; And composition thereof.In some embodiments, further process can using the generation of C15-C18 lipid acid and/or ester as target.In other embodiments, further process can using the generation of diacid and/or diester as target.In other embodiment again, process can be greater than the generation of the compound of stearic acid and/or linolenic molecular weight as target using having molecular weight further.
As shown in fig. 1, for the overhead product alkene 32 from separating unit 30, alkene 32 can be separated further or distill to be separated various component in separation of olefins unit 40.Separation of olefins unit 40 can comprise multiple distillation tower.In some embodiments, at least four distillation towers are used to be separated various component streams.In other embodiments, three or less tower are for separating of olefin component.
In one embodiment, the lighting end alkene 44 primarily of C2-C9 compound composition can be distilled to column overhead stream from separation of olefins unit 40.In some embodiments, lighting end alkene 44 major part is made up of C3-C8 hydrocarbon compound.In other embodiments, the comparatively heavy olefins with higher carbon number can be separated in lighting end olefin stream 44 at tower top, to contribute to using specific fuel composition as target.Lighting end alkene 44 can be recycled to double decomposition reactor 20, removes and be used for process further and sell from system, or the combination of the two.In one embodiment, lighting end alkene 44 can partly be removed and partly be recycled to double decomposition reactor 20 from system.About other logistics in separation of olefins unit 40, can be used as alkene bottoms 46 compared with C16+, C18+, C20+, C22+ or C24+ compound stream of heavy and separate.This alkene bottoms 46 can be eliminated or be recycled to double decomposition reactor 20 for further process, or the combination of the two.In another embodiment, middle runnings olefin stream 42 can distill unit from alkene and separates for further process.Middle runnings alkene 42 can be designed to be used for carbon number range selected by special fuel composition as target.As limiting examples, C5-C15 distribution can be used for being further processed as naphtha type rocket engine fuel as target.Alternatively, C8-C16 distribution can be used for being further processed as kerosene type jet fuel as target.In another embodiment, C8-C25 distribution can be used for being further processed as diesel oil fuel as target.
In some embodiments, treatment step can be carried out to maximize alhpa olefin purity.In other embodiments, treatment step can be carried out to maximize C10 alkene purity.Such as, the C10+ alkene from separating unit 30 or specific olefin stream thing can react to improve C10 alkene purity with ethene under the existence of metathesis catalyst in secondary (secondary) double decomposition reactor.In one embodiment, metathesis catalyst is rhenium oxide catalysts (such as, being carried on the rhenium oxide on aluminum oxide).In another embodiment, metathesis is tungsten oxide catalyst (such as, being carried on the Tungsten oxide 99.999 on silicon-dioxide).This replacement(metathesis)reaction can be carried out in fixed-bed reactor.In some embodiments, ethylene reagent recirculation can get back to time double decomposition reactor.Comparatively light olefin (C4-C9) from secondary double decomposition reactor can be used for the main double decomposition reactor olefin from separating unit 30 processing further.
In some embodiments, alkene 32 can be oligomeric to form poly-alpha olefins (PAO) or poly-internal olefin (PIO), mineral oil substitute and/or biodiesel fuel.Oligomerization can occur after distillation unit 30 or after overhead product separation of olefins unit 40.In some embodiments, the by product from oligomerization recirculation can get back to double decomposition reactor 20 for further process.
In other embodiments, alkene 32, lighting end alkene 44 or middle runnings alkene 42 can under the existence of metathesis catalyst in secondary double decomposition reactor self-metathesis to produce heavier C14+, C16+ or C18+ olefin product.In one embodiment, metathesis catalyst is rhenium oxide catalysts (such as, being carried on the rhenium oxide on aluminum oxide).In another embodiment, metathesis is tungsten oxide catalyst (such as, being carried on the Tungsten oxide 99.999 on silicon-dioxide).This replacement(metathesis)reaction can be carried out in fixed-bed reactor.Heavier C14+, C16+ or C18+ alkene can be used as tensio-active agent or glossy lubricating oil.In some embodiments, the comparatively light olefin by product from self-metathesis reaction recirculation can get back to time double decomposition reactor or main double decomposition reactor 20 for further process.
In some embodiments, alkene 32, middle runnings alkene 42, lighting end alkene 44 or alkene bottoms 46 can before hydrogenation unit 50 pre-treatment to remove potential catalyzer poison.Example (such as sorbent material, aluminum oxide or heat) for the potential raw materials pretreatment of olefin stream describes about the potential process of natural oil 12 above.
As mentioned above, in one embodiment, the alkene 32 from separating unit 30 can directly deliver to hydrogenation unit 50.In another embodiment, hydrogenation unit 50 can be delivered to from the middle runnings alkene 42 of separation of olefins unit 40, lighting end alkene 44 or alkene bottoms 46.Hydrogenation can be carried out for any currently known methods of the double bond containing compound of hydrogenation such as alkene 32, middle runnings alkene 42, lighting end alkene 44 or alkene bottoms 46 according in this area.In some embodiments, in hydrogenation unit 50, hydrogen 48 and alkene 32, middle runnings alkene 42, lighting end alkene 44 or alkene bottoms 46 react to produce hydrogenated products 52 in the presence of a hydrogenation catalyst.Discuss typical hydrogenation catalyst and reaction conditions above.During hydrogenation, the compound of the carbon-carbon double key in alkene is part, selectivity or completely saturated compound by hydrogen 48 hydrogenation.
In one embodiment, gained hydrogenated products 52 comprises the hydrocarbon of the distribution had centered by about C10-C12 hydrocarbon for petroleum naphtha and kerosene type jet fuel composition.In another embodiment, distribute centered by about C16-C18 for diesel fuel composition.
In other embodiments, olefine selective ground hydrogenation is to reduce the existence of many unsaturated olefins and to increase the existence of cholesterol alkene.Alkene 32 from separating unit 30 can comprise polyene hydrocarbon (such as, diene or triolefin), and wherein polyunsaturated amount depends on the intrinsiccharacteristic of natural oil 12.Relative to cholesterol olefin(e) compound, many unsaturated olefins such as diene and triolefin can cause a large amount of problem to downstream processing and final utilization.The rate of oxidation of diene and triolefin can be the 10-100 of cholesterol alkene doubly.These oxidation productss will make some materials be unsuitable for some application such as senior oil field and reclaim (advancedoilfieldrecovery).Therefore, it is useful for reducing provable from the polyunsaturated amount in the alkene 32 of separating unit 30.Meanwhile, alkene may be more valuable than paraffinic components.Therefore, in some embodiments, partly or optionally how unsaturated hydrogenation is and form cholesterol alkene with removing for alkene 32, lighting end alkene 44, middle runnings alkene 42 or alkene bottoms 46.Typical reaction conditions such as temperature, pressure, reaction times and hydrogenation catalyst type describe about the part of metathesis product 22 or selective hydration above.
Part or selective hydration olefin product 52 can be used for preparation table surface-active agent/surfactant precursor, include but not limited to linear alkylbenzene.In some embodiments, part or selective hydration product 52 can be used for but be not limited to senior oil field reclaiming or drilling fluid.
In some embodiments, in diene selective hydration, can be at least 50%, at least 75%, at least 85%, at least 95% or at least 98% from many unsaturated olefins to paraffinic hydrocarbons and cholesterol conversion of olefines rate.Selectivity to cholesterol alkene instead of paraffinic hydrocarbons is at least 90%, at least 95%, at least 99% or at least 99.5%.
In some embodiments, completely, after part or selective hydration, technology known in the art (such as, by filtering) can be used from hydrogenated products 52 to remove hydrogenation catalyst.In some embodiments, board-like those removing hydrogenation catalysts that such as can be purchased from SparklerFilters, Inc., ConroeTX with frame-type filter are used.In some embodiments, filter by means of pressure or vacuum.In order to improve strainability, flocculating aids can be used.Flocculating aids directly can be added product or be applied to strainer.The representative limiting examples of flocculating aids comprises diatomite, silicon-dioxide, aluminum oxide and carbon.Typically, with about 10 % by weight or less, such as about 5 % by weight or less about 1 % by weight or less amount use flocculating aids.Also other filtering techniques and flocculating aids can be adopted to remove the hydrogenation catalyst used.In other embodiments, use centrifugal, decant product subsequently, remove hydrogenation catalyst.
In some embodiments, based on the quality (quality) of hydrogenated products 52 produced in hydrogenation unit 50, can preferably isomerizing olefins hydrogenated products 52 to contribute to required product characteristics such as flash-point, zero pour, energy density, cetane value or terminal distillation temperature and other parameters as target.Isomerization reaction is well known in the art, as U.S. Patent number 3, and 150,205; 4,210,771; 5,095,169; With 6,214, described in 764, its full content is incorporated herein by reference.In one embodiment, also can some remaining C15+ compounds of cracking in the isomerization reaction in this stage, it can contribute to producing the fuel composition of the compound with required carbon number range (such as the 5-16 of jet fuel compositions) further.
In some embodiments, isomerization can occur with the step of hydrogenation in hydrogenation unit 50 simultaneously, thus using required product as target.In other embodiments, can there is (that is, alkene 32 or middle runnings alkene 42 can isomerization before hydrogenation unit 50) in isomerization steps before step of hydrogenation.In other embodiment again, be below possible: in the scope of the low molecular weight olefins 14 used in based on replacement(metathesis)reaction and/or the selection of middle-molecular-weihydroxyethyl alkene 15, can avoid or reduce isomerization steps.
In some embodiments, hydrogenated products 52 is part or selective hydration product stream, it comprises the C7 of about 15-25 % by weight, the C8 of about <5 % by weight, the C9 of about 20-40 % by weight, the C10 of about 20-40 % by weight, the C11 of about <5 % by weight, the C12 of about 15-25 % by weight, the C13 of about <5 % by weight, the C14 of about <5 % by weight, the C15 of about <5 % by weight, the C16 of about <1 % by weight, the C17 of about the <1 % by weight and C18+ of about <1 % by weight.
As shown in fig. 1, hydrogenated products 52 can process further, remove any residue by product from hydrogenated products 52 in separating unit 60, and such as hydrogen, water, lighting end C2-C9 hydrocarbon or C15+ hydrocarbon, produce objective composition thus.Separating unit 60 can comprise multiple distillation tower.In some embodiments, at least four distillation towers are used to be separated each component streams.In other embodiments, three or less tower is used.
In one embodiment, hydrogenated products 52 is separable into multi-products cut, such as C9-C15 product 64, lighting end C2-C9 fraction 62 and/or C15+ last running fraction 66.Distillation can be used for being separated described fraction.Alternatively, in other embodiments, last running fraction 66 is by being separated with C9-C15 product 64 as follows: hydrogenated products 52 is cooled to about-40 DEG C ,-47 DEG C or-65 DEG C and then such as filtered by technology known in the art, decant or the solid-state last running fraction 66 of centrifugal removing.
About the ester 34 from distillation unit 30, in some embodiments, ester 34 can be used as ester products logistics 36 and all extracts also process further or sell because himself is worth, as shown in fig. 1.As limiting examples, ester 34 can comprise the multiple triglyceride level that can be used as lubricant.Based on the disintegrate-quality (quality) between alkene and ester, ester 34 can comprise some comparatively heavy olefin component of being carried by triglyceride level.In other embodiments, such as, ester 34 can process further in the concise or other chemistry of biology known in the art or fuel, produces multi-products such as biofuel or the specialty chemicals that are worth higher than triglyceride level thus.Alternatively, in some embodiments, ester 34 can partly extract and sell from system, and wherein remainder processes further in the concise or other chemistry of biology known in the art or fuel.
In some embodiments, ester 34 can carry out pre-treatment before further processing to remove potential catalyzer poison.Example (such as sorbent material, aluminum oxide or heat) for the potential raw materials pretreatment of ester 34 describes about the potential process of natural oil 12 above.
In some embodiments, ester 34 optionally hydrogenation to reduce the existence of many unsaturated ester and to increase the existence of cholesterol ester.Typical reaction conditions such as temperature, pressure, reaction times and hydrogenation catalyst type describe about the selective hydration of metathesis product 22 above.
In some embodiments, in diene selective hydration, can be at least 50%, at least 75%, at least 85%, at least 95% or at least 98% from many unsaturated ester to saturated and transformation efficiency that is cholesterol ester.Selectivity to cholesterol ester instead of saturated ester is at least 90%, at least 95%, at least 99% or at least 99.5%.
In some embodiments, transesterify unit 70 is delivered in ester logistics 34 (in some embodiments, its selective hydration).In transesterify unit 70, ester 34 and at least one alcohol 38 react under the existence of transesterification catalyst.In some embodiments, alcohol comprises methyl alcohol and/or ethanol.In another embodiment, alcohol 38 comprises glycerine (and transesterification reaction is glycerolysis reaction).In one embodiment, transesterification reaction is carried out under about 60-70 DEG C and about 1atm.In some embodiments, transesterification catalyst is the sodium methoxide catalyst of homogeneous phase.Can use the catalyzer of different amount in the reaction, and in some embodiments, transesterification catalyst exists with the amount of the about 0.5-1.0 % by weight of ester 34.
In some embodiments, transesterification reaction can produce the ester exchange offspring 72 comprising the monomer terminal olefine ester with following structure:
Wherein X is saturated or undersaturated alkyl (alkyl) chain of C3-C18, and R is alkyl.In some embodiments, R is methyl.
Transesterification reaction can produce the ester exchange offspring 72 comprising saturated and/or unsaturated monomer fatty acid methyl ester (" FAME "), glycerine, methyl alcohol and/or free fatty acids.In some embodiments, ester exchange offspring 72 or its fraction can be configured for the source of biofuel.In some embodiments, ester exchange offspring 72 comprises C10-C15 or C11-C14 ester.In some embodiments, ester exchange offspring 72 comprises 9DA ester, 9UDA ester and/or 9DDA ester.The limiting examples of 9DA ester, 9UDA ester and 9DDA ester comprises 9-decenoate (" 9-DAME "), 9-methyl undecylenate (" 9-UDAME ") and 9-dodecenoic acid methyl esters (" 9-DDAME ") respectively.As limiting examples, in transesterification reaction, the 9DA part of metathetic glyceryl ester removes to form 9DA ester from glycerol backbone.
As discussed above, the type of the ester exchange offspring formed is based on the reactant entering double decomposition reactor 20.In a particular implementation, the downstream of the replacement(metathesis)reaction between 3-hexene and natural oil produces C12 methyl esters (9-DDAME).
In another embodiment, glyceryl alcohol can be used for the reaction of glyceryl ester logistics.This reaction can produce monoglyceride and/or triglyceride.
In some embodiments, the ester exchange offspring 72 from transesterify unit 70 can be delivered to liquid-liquid separation unit, wherein ester exchange offspring 72 (that is, FAME, free fatty acids and/or alcohol) is separated from glycerine.In addition, in some embodiments, glycerin by-products logistics can process further in secondary (secondary) separating unit, wherein deglycerizin and transesterify unit 70 is got back in any remaining alcohol recirculation be used for further process.
In some embodiments, ester exchange offspring 72 can be delivered to hydrogenation unit and be used for selective hydration, wherein be increased the concentration of cholesterol ester by diene-selective hydration.Typical reaction conditions such as temperature, pressure, reaction times and hydrogenation catalyst type describe about the selective hydration of metathesis product 22 above.
In some embodiments, in diene selective hydration, can be at least 50%, at least 75%, at least 85%, at least 95% or at least 98% from many unsaturated ester of transesterify to the transformation efficiency of saturated and monounsaturated transesterify ester.Selectivity to cholesterol ester instead of saturated ester is at least 90%, at least 95%, at least 99% or at least 99.5%.
In one embodiment, ester exchange offspring 72 processes further in water-washing unit.In this unit, when washing with water, ester exchange offspring stands liquid-liquid extraction.Excessive alcohol, water and glycerine remove from ester exchange offspring 72.In another embodiment, be drying unit after water-washing step, wherein excessive water removes from required ester mixture (that is, specialty chemicals) further.Such specialty chemicals comprise limiting examples such as 9DA, 9UDA and/or 9DDA, aforesaid an alkali metal salt and alkaline earth salt, combine individually or with it.
In one embodiment, monomer specialty chemicals (such as, 9DA) can process to form lactone further in oligomerization, and it can be used as the precursor of tensio-active agent.
In some embodiments, the ester exchange offspring 72 from transesterify unit 70 or the specialty chemicals from water-washing unit or drying unit are delivered to ester distillation tower 80 and is used for being separated various independent compound or compound group further, as shown in fig. 1.This separation can include, but not limited to the separation of 9DA ester, 9UDA ester and/or 9DDA ester.In one embodiment, 9DA ester 82 can distillation or be separated separately from the remaining mixture 84 of ester exchange offspring or specialty chemicals.In some processing condition, 9DA ester 82 should be component the lightest in ester exchange offspring or specialty chemicals logistics, and at the top of ester distillation tower 80 out.In another embodiment, ester exchange offspring or specialty chemicals remaining mixture 84 or can separate in the bottom end of tower compared with heavy component.In some embodiments, this bottoms 84 can be sold as biofuel potentially.
9DA ester, 9UDA ester and/or 9DDA ester can process further after the distilation steps of ester distillation tower.In one embodiment, under known operational condition, then 9DA ester, 9UDA ester and/or 9DDA ester can stand with the hydrolysis reaction of water to form 9DA, 9UDA and/or 9DDA, aforesaid an alkali metal salt and alkaline earth salt, combine individually or with it.
In some embodiments, from the monomeric fatty acid esters mutually reactive of ester exchange offspring 72 to form other specialty chemicals such as dimer.
In other embodiments, certain esters product such as 9DDA methyl esters is by the subsequent disposal of ester exchange offspring and reactions steps and enrichment.In one embodiment, the logistics of C10 methyl esters can be separated from the C12+ methyl esters compared with heavy.Then the logistics of C10 methyl esters can react to form C12 methyl esters and ethene with 1-butylene under the existence of metathesis catalyst.Ethene can be separated from methyl esters and C10 and C12 methyl esters can be removed or be back to ester distillation tower for further process.
In some embodiments, from the fatty acid monomer of ester exchange offspring 72 and/or the isomerization of monomeric fatty acid esters to form isomerized fatty acid monomer and/or isomerized monomeric fatty acid esters.Can carry out at the temperature (that is, being greater than 25 DEG C) raised from the lipid acid of ester exchange offspring 72 and/or the isomerization of fatty acid ester.In some embodiments, the thermal treatment temp of isomerization reaction is greater than 100 DEG C, is greater than 150 DEG C or be greater than 200 DEG C.In other embodiments, temperature be 100 DEG C-300 DEG C, 150-250 DEG C or about 200 DEG C.In some embodiments, heat treatment step carries out under the existence of isomerization catalyst.In an embodiment, isomerization catalyst is (PCy 3) 2(Cl) (H) Ru (CO), wherein " Cy " represents cyclohexyl.
In some embodiments, the fatty acid monomer and/or the monomeric fatty acid esters that stand isomerization reaction are selected from: 9DA, 9DA ester, 9UDA, 9UDA ester, 9DDA and 9DDA ester.The isomerization of lipid acid and/or fatty acid ester can produce and be selected from following isomerized fatty acid monomer and/or isomerized monomeric fatty acid esters: isomerized 9DA, isomerized 9DA ester, isomerized 9UDA, isomerized 9UDA ester, isomerized 9DDA and isomerized 9DDA ester.
Make fatty acid monomer and/or the isomerization of monomeric fatty acid esters can improve multiple performance.Such as, isomerized product compositions can be observed broadening of zero pour and fusing point, this can allow to transport isomerized lipid acid/ester products composition with the concentration of higher fatty acid monomer and/or monomeric fatty acid esters, and does not cause shipping (transport) problem.
Isomerized fatty acid monomer and/or isomerized monomeric fatty acid esters can be used in multiple different commercial applications; include, but are not limited to: lubricant, wax, film, paint, paint remover, coating, softening agent, resin, tackiness agent, solvent, polyvalent alcohol, soil stabilization, chemical grouting, oil field drilling fluids, crop protection products, tensio-active agent, intermediate and tackiness agent.
In some embodiments, ester exchange offspring 72 comprises terminal olefine ester and under the existence of metathesis catalyst, carries out cross metathesis with internal olefin to produce diprotic acid and/or dibasic ester and olefin by-products.As mentioned above, ester exchange offspring 72 can comprise the terminal olefine with following structure:
Wherein X is saturated or undersaturated alkyl (alkyl) chain of C3-C18, and R is alkyl or hydrogen.
In some embodiments, terminal olefine-internal olefin cross-metathesis carries out with the weight ratio of 1:99 (end: interior) to 99:1 (end: interior).In other embodiments, the weight ratio of terminal olefine and internal olefin is 1:5-5:1.In other embodiment again, the weight ratio of terminal olefine and internal olefin is 1:2-2:1.In an embodiment, the weight ratio of terminal olefine and internal olefin is about 1:1.
In some embodiments, terminal olefine is selected from: 4-pentenoate, 5-hexene acid esters, 6-heptenoic acid esters, 7-octene acid esters, 8-nonenoate, 9-decenoate, Shiyixisuan Undecylenic Acid ester, 11-dodecylene acid esters, 12-tridecylene acid esters, 13-tetradecenoic acid acid esters, 14-pentadecylenic acid ester, 15-cetene acid esters, 16-heptadecene acid esters, 17-vaccenic acid acid esters, its acid, and composition thereof.In an embodiment, terminal olefine is 9-decenoate.
In some embodiments, terminal olefine be selected from following internal olefin and carry out cross metathesis: pentenoate, hexene acid esters, heptenoic acid esters, octene acid esters, nonenoate, decenoate, undecylenate, dodecylene acid esters, tridecylene acid esters, tetradecenoic acid acid esters, pentadecylenic acid ester, cetene acid esters, heptadecene acid esters, vaccenic acid acid esters, its acid, and composition thereof.In an embodiment, internal olefin is 9-undecylenate.In another embodiment, internal olefin is 9-dodecylene acid esters.
In some embodiments, by making to react under a part of terminal olefine ester of ester exchange offspring 72 and lower molecular weight internal olefin or the existence of middle-molecular-weihydroxyethyl internal olefin at metathesis catalyst to form internal olefin.In some embodiments, lower molecular weight internal olefin is selected from: 2-butylene, 2-amylene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene, 2-nonene, 3-nonene, 4-nonene and composition thereof.In an embodiment, lower molecular weight internal olefin is 2-butylene.In another embodiment, lower molecular weight internal olefin is 3-hexene.
In some embodiments, at least 70 % by weight, 80 % by weight or 90 % by weight dibasic ester and/or diprotic acid formed by the cross-metathesis of terminal olefine and internal olefin under the existence of catalyzer being less than 150ppm, 100ppm, 50ppm, 25ppm or 10ppm.Under similar reaction conditions, the self-metathesis reaction of comparable employing terminal olefine (such as 9-decenoate) can need more catalyzer (such as, be greater than 150ppm or be greater than 500ppm) to realize similar dibasic ester and/or diprotic acid output (potentially owing to forming Crude products.deep process).
In some embodiments, be separated in from metathesis product the olefin by-products formed cross-metathesis when being undertaken by the reaction between terminal olefine and internal olefin and improve dibasic ester and/or dihydric acid output.In other embodiments, by improving dibasic ester and/or diprotic acid output by the metathesis product in chemically inactive gas (such as nitrogen, argon gas or helium) bubbling double decomposition reactor to make the ventilation of the gas dissolved/by product (such as, olefin by-products) in metathesis product (ventilate).
In some embodiments, the cross-metathesis of terminal olefine and internal olefin produces the dibasic ester comprising following structure:
Wherein R and R ' is alkyl or aryl independently, and Y is the alkene comprising 6-36 carbon atom.In some embodiments, cross-metathesis forms C21-C24 dibasic ester.In one embodiment, cross-metathesis forms dibasic ester, and wherein R and R ' is for methyl and Y is 8-cetene (that is, the dibasic ester formed by the cross-metathesis of terminal olefine and internal olefin is 9-octadecene diacid dimethyl ester).In some embodiments, these dibasic esters by optionally hydrogenation to increase the concentration of cholesterol dibasic ester.
In some embodiments, the dibasic ester deriving from ester exchange offspring 72 can to stand with the hydrolysis reaction of water to form the diprotic acid with following structure further:
Wherein Y is the alkene comprising 6-36 carbon atom.In one embodiment, Y is 8-cetene (that is, diprotic acid is 9-octadecene diacid).
After hydrolysis, in some embodiments, product stream can deliver to flashing tower or decanting vessel with from diprotic acid removing first alcohol and water.
In other embodiments, diprotic acid and/or dibasic ester isomerization are to form isomerized diprotic acid and/or isomerized dibasic ester.The isomerization of diprotic acid and/or dibasic ester can be carried out at the temperature (that is, being greater than 25 DEG C) raised.In some embodiments, the thermal treatment temp of isomerization reaction is greater than 100 DEG C, is greater than 150 DEG C or be greater than 200 DEG C.In other embodiments, temperature be 100 DEG C-300 DEG C, 150-250 DEG C or about 200 DEG C.In some embodiments, heat treatment step carries out under the existence of isomerization catalyst.In an embodiment, isomerization catalyst is (PCy 3) 2(Cl) (H) Ru (CO), wherein " Cy " represents cyclohexyl.
In some embodiments, isomerized diprotic acid and/or isomerized dibasic ester comprise and are selected from following compound: isomerized 9-octadecene diacid dimethyl ester or isomerized 9-octadecene diacid.
In some embodiments, isomerized diprotic acid and/or isomerized dibasic ester carry out self-metathesis or carry out cross metathesis with low molecular weight olefins or middle-molecular-weihydroxyethyl alkene.Hereafter discuss typical metathesis reaction conditions and catalyzer in more detail.In one embodiment, isomerized diprotic acid and/or isomerized dibasic ester about 10ppm, 20ppm, 40ppm, 50ppm, 80ppm, 100ppm, 120ppm or be greater than 150ppm metathesis catalyst existence under carry out self-metathesis.
In some embodiments, by isomerized lipid acid, isomerized fatty acid ester, diprotic acid, dibasic ester, isomerized diprotic acid and/or the complete hydrogenation of isomerized dibasic ester.Typical hydrogenation condition and catalyzer are discussed above.In an embodiment, hydrogenation carries out under the existence of the catalyzer based on nickel under about 150 DEG C and 150psig.In another embodiment, hydrogenation carries out under the existence of the catalyzer based on nickel under about 150 DEG C and 100psig.In some embodiments, these binary materials optionally hydrogenation to increase the concentration of cholesterol compound.
As noted, under the existence of metathesis catalyst, there is the cross metathesis between the self-metathesis of natural oil, natural oil and low molecular weight olefins or middle-molecular-weihydroxyethyl alkene or the cross metathesis between terminal olefine and internal olefin.As previously mentioned, term " metathesis catalyst " comprises any catalyzer or the catalyst system of catalysed metathesis reaction.Any metathesis catalyst that is known or following exploitation can use individually or with one or more other catalyst combination.Non-restrictive illustrative metathesis catalyst and processing condition are described in the 18-47 page of PCT/US2008/009635, and it is incorporated herein by reference.Shown a large amount of metathesis catalysts are manufactured by Materia, Inc. (Pasadena, CA).
Metathesis process can be enough to carry out under any condition producing required metathesis product.Such as, stoichiometry, atmosphere, solvent, temperature and pressure can be selected produce required product and minimize less desirable by product by those skilled in the art.Metathesis process can carry out under an inert atmosphere.Similarly, if reagent provides with gas, inert gas diluent can be used.Inert atmosphere or inert gas diluent typically are rare gas element, mean gas and can not interact to hinder catalysis in fact with metathesis catalyst.Such as, concrete rare gas element is selected from helium, neon, argon gas, nitrogen, combines individually or with it.
In some embodiments, before carrying out replacement(metathesis)reaction, metathesis catalyst is dissolved in solvent.In some embodiments, it is inertia in fact that selected solvent may be selected to be for metathesis catalyst.Such as, the solvent of inertia comprises ad lib in fact: aromatic hydrocarbons, such as benzene,toluene,xylene etc.; Halogenated aryl hydrocarbon, such as chlorobenzene and dichlorobenzene; Aliphatic solvents, comprises pentane, hexane, heptane, hexanaphthene etc.; And chloroparaffin, such as methylene dichloride, chloroform, ethylene dichloride etc.In an embodiment, solvent comprises toluene.
In other embodiments, before carrying out replacement(metathesis)reaction, metathesis catalyst is not dissolved in solvent.Alternatively, catalyzer and natural oil 12 can be made slurry, wherein natural oil 12 is liquid.Under these conditions, solvent (such as, toluene) and the loss eliminating the downstream olefin when being separated solvent may be eliminated from process.In other embodiments, can by metathesis catalyst in solid form (and not being make slurry) add natural oil 12 (such as, with spiral charging).
Replacement(metathesis)reaction temperature can be rate-controlling variable, and wherein selective temperature provides required product with acceptable speed.In some embodiments, replacement(metathesis)reaction temperature is greater than about-40 DEG C, is greater than about-20 DEG C, is greater than about 0 DEG C or be greater than about 10 DEG C.In some embodiments, replacement(metathesis)reaction temperature is less than about 150 DEG C or be less than about 120 DEG C.In one embodiment, replacement(metathesis)reaction temperature is about 10 DEG C of-Yue 120 DEG C.
Replacement(metathesis)reaction can be run under any required pressure.Typically, expect to maintain total pressure enough high to keep cross-metathesis thing (reagent) in dissolved state.Therefore, along with the molecular weight of cross-metathesis thing increases, lower pressure range typically reduces, because the boiling point of cross-metathesis thing increases.Total pressure may be selected to be and is greater than about 0.1atm (10kPa), is greater than about 0.3atm (30kPa) in some embodiments or is greater than about 1atm (100kPa).Typically, reaction pressure is not more than about 70atm (7000kPa), is not more than about 30atm (3000kPa) in some embodiments.The non-restrictive illustrative pressure range of replacement(metathesis)reaction is about 1atm (100kPa)-Yue 30atm (3000kPa).
Partial hydrogenation can be used to produce for multi-purpose compound.Such as, in some embodiments, method disclosed herein is used for partly hydrogenated olefins sample, such as comprises C15 alkene, C18 alkene or its olefin samples combined.In some such embodiments, olefin samples comprises at least 40% weight or at least 50% weight, is up to 60% weight or is up to the C15 alkene of 70% weight.In some such embodiments, olefin samples comprises at least 20% weight or at least 30% weight, is up to 50% weight or is up to the C18 alkene of 60% weight.After by method hydrogenation disclosed herein, compositions of olefines has and is not more than 10% weight or is not more than 7%% weight or is not more than the polyene content of 5% weight, based on the gross weight of alkene in composition.In some such embodiments, compositions of olefines has the monoene content of at least 85% weight or at least 90% weight.
Partially hydrogenated C15-C18 compositions of olefines like this can be suitable for using in many ways.Such as, because such composition toxicity compared with having the composition of higher polyene content is less and more can biological degradation, therefore they can be suitable for various oil field application, and such as down-hole (downhole) drilling fluid, especially for offshore drilling.Therefore, in some embodiments, present disclosure provides the method for process oil well, comprise: the C15-C18 compositions of olefines (or the composition containing such C15-C18 compositions of olefines (such as with external phase)) according to any above-mentioned embodiment is placed in oil well, such as during drilling well, or between drilling circulation, or before drilling well.
Although as described in the present invention can have amendment and alternative form, described its numerous embodiments in detail.However, it should be understood that the description of these numerous embodiments is herein not intended to limit the present invention, but on the contrary, the present invention is for containing all modifications, equivalent and the surrogate in the spirit and scope of the present invention that fall into and be defined by the claims.In addition, although also describe the present invention with reference to following non-limiting example, certainly will understand, the present invention is not limited thereto, due to those skilled in the art, especially according to above-mentioned instruction, can modify.
Embodiment
embodiment 1 – PRICATCU50/8P selective hydration C9/C10 alkene
In 600mLParr reactor, 300gC9/C10 raw material (C9 of 88.0%, the C10 of 10.5%) and 1.52gPRICATCU50/8P (0.5 % by weight) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 900rpm of gas dispersion impeller.Monitoring H 2reactor also recharges to 100psig when it is down to 50psig by pressure.Blend sample is answered negate in 30,60,120,180 and 240 minutes.Use GC monitors both the polyenoid disappearance and paraffinic hydrocarbons and the formation of cholesterol alkene of reacting.Reaction proceeded to 95% transformation efficiency in 2 hours, had 92% selectivity to cholesterol olefin product (C9:1, C10:1).Reaction mixture is carried out gravity filtration and collects limpid product.
embodiment 2 – PRICAT9908 selective hydration C9/C10 alkene
In 600mLParr reactor, 300gC9/C10 raw material (C9 of 88.0%, the C10 of 10.5%) and 0.74gPRICAT9908 (0.25 % by weight, deglycerizin three ester before reaction) are used N 2, then H 2purge each 15 minutes, then at 150 DEG C, 100psigH 2lower reaction is stirred with the 900rpm of gas dispersion impeller.Monitoring H 2reactor also recharges to 100psig when it is down to 50psig by pressure.Blend sample is answered negate in 30,60,120,180 and 240 minutes.Use GC monitors both the polyenoid disappearance and paraffinic hydrocarbons and the formation of cholesterol alkene of reacting.Reaction carried out 85% transformation efficiency in 30 minutes, had 95% selectivity to cholesterol alkene (C9:1, C10:1).Reaction mixture is carried out gravity filtration and collects limpid product.
the C12 alkene that embodiment 3 – is purified with PRICAT9908 selective hydration
In 600mLParr reactor, 300gC12 raw material (by alumina column and molecular sieve purification, the C12 of 99.6%) and 0.31gPRICAT9908 (0.1 % by weight, deglycerizin three ester before reaction) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure, and when it is down to 50psig, reactor is recharged to 100psig.Blend sample is answered negate in 15,30,45,60 and 75 minutes.GC is used to monitor the disappearance of C12:2 diene and the formation of C12:0 paraffinic hydrocarbons and C12:1 monoene.Reaction carried out 96.5% transformation efficiency in 30 minutes, had 98.4% selectivity to C12:1.Reaction mixture is carried out gravity filtration, and collects limpid product.
embodiment 4 – PRICAT9908 and PRICATCU50/8P selective hydration purifying c12 alkene
In 600mLParr reactor, 300gC12 raw material (by alumina column and molecular sieve purification, the C12 of 99.6%), 0.30gPRICAT9908 (0.1 % by weight) and 0.02gPRICATCU50/8P (0.005 % by weight) are used N 2, then H 2purge each 15 minutes.Then at 180 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure, and when it is down to 50psig, reactor is recharged to 100psig.Response sample is got at 15,30,45 and 60 minutes.GC is used to monitor the disappearance of C12:2 diene and the formation of C12:0 paraffinic hydrocarbons and C12:1 monoene.Reaction carried out 94.3% transformation efficiency in 30 minutes, had 97.6% selectivity to C12:1.Reaction mixture is carried out gravity filtration, and collects limpid product.
embodiment 5 – PRICATCU50/8P and PRICAT9908 selective hydration purifying c12 alkene
In 600mLParr reactor, 300gC12 raw material (by alumina column and molecular sieve purification, the C12 of 99.6%), 0.90gPRICATCU50/8P (0.30 % by weight) and 0.05gPRICAT9908 (0.015 % by weight) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 100rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.Blend sample is answered negate in 15,30,45,60 and 75 minutes.GC is used to monitor the disappearance of C12:2 diene and the formation of C12:0 paraffinic hydrocarbons and C12:1 monoene.Reaction carried out 96.7% transformation efficiency in 30 minutes, had 92.9% selectivity to C12:1.Reaction mixture is carried out gravity filtration, and collects limpid product.
the C12 alkene that embodiment 6 – is purified with PRICATCU50/8P selective hydration
In 600mLParr reactor, 300gC12 raw material (by alumina column and molecular sieve purification, the C12 of 99.6%) and 0.90gPRICATCU50/8P (0.30 % by weight) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 100rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.Blend sample is answered negate in 15,30,45 and 60 minutes.GC is used to monitor the disappearance of C12:2 diene and the formation of C12:0 paraffinic hydrocarbons and C12:1 monoene.Reaction proceeded to 98.6% transformation efficiency in 30 minutes, had 99.7% selectivity to C12:1.Reaction mixture is carried out gravity filtration, and collects limpid product.
the C12 alkene that embodiment 7 – is purified with PRICATCU50/8P selective hydration
In 600mLParr reactor, 300gC12 raw material (by alumina column and molecular sieve purification, the C12 of 99.6%) and 0.90gPRICATCU60/35P (0.30 % by weight) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 100rpm of gas dispersion impeller.Monitoring H 2pressure, and when it is down to 50psig, reactor is recharged to 100psig.Blend sample is answered negate in 15,30,45,60 and 90 minutes.GC is used to monitor the disappearance of C12:2 diene and the formation of C12:0 paraffinic hydrocarbons and C12:1 monoene.Reaction proceeded to 73.3% transformation efficiency in 90 minutes, had 99.4% selectivity to C12:1.Reaction mixture is carried out gravity filtration, and collects limpid product.
embodiment 8 – is by alumina column purifying C12/C13 alkene
In order to purification of samples, by C12/C13 raw material by activated alumina column, then at N 2under atmosphere dried overnight on molecular sieve.Peroxide number is reduced to 1.90meq/mg, and as KarlFisher volumetry the water-content that measures be reduced to 49.77ppm.
the C12/C13 alkene that embodiment 9 – is purified with PRICATCU9908 selective hydration
In 600mLParr reactor, 300gC12/C13 raw material (by alumina column and molecular sieve purification, the C12 of 93.4%, the C13 of 4.4%) and 0.30gPRICAT9908 (0.10 % by weight, deglycerizin three ester before reaction) are used N 2, then H 2purge each 15 minutes, then at 150 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.Blend sample is answered negate in 30,60,90 and 120 minutes.The disappearance of diene (C12:2 and C13:2) and the formation of monoene (C12:1 and C13:1) and paraffinic hydrocarbons (C12:0 and C13:0) is monitored by GC.Reaction proceeded to 78.3% transformation efficiency in 90 minutes, had 94.0% selectivity to cholesterol olefin product.Reaction mixture is carried out gravity filtration and collects limpid product.
the C12/C13 alkene that embodiment 10 – is purified with PRICATCU50/8P selective hydration
In 600mLParr reactor, 300gC12/C13 raw material (by alumina column and molecular sieve purification, the C12 of 93.4%, the C13 of 4.4%) and 0.90gPRICATCU50/8P (0.30 % by weight) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.Blend sample is answered negate in 30 and 45 minutes.GC is used to monitor the disappearance of diene (C12:2 and C13:2) and the formation of monoene (C12:1 and C13:1) and paraffinic hydrocarbons (C12:0 and C13:0).Reaction proceeded to 97.7% transformation efficiency in 30 minutes, had 97.2% selectivity to cholesterol olefin product.Reaction mixture is carried out gravity filtration and collects limpid product.
the C12/C13 alkene that embodiment 11 – is purified with PRICATCU50/8P selective hydration
In 600mLParr reactor, 300gC12/C13 raw material (by alumina column and molecular sieve purification, the C12 of 93.4%, the C13 of 4.4%) and the reacted PRICATCU50/8P (0.44 % by weight) once of 1.33g are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.Blend sample is answered negate in 30 and 60 minutes.GC is used to monitor the disappearance of diene (C12:2 and C13:2) and the formation of monoene (C12:1 and C13:1) and paraffinic hydrocarbons (C12:0 and C13:0).Reaction proceeded to 93.2% transformation efficiency in 60 minutes, had 98.2% selectivity to cholesterol olefin product.Reaction mixture is carried out gravity filtration and collects limpid product.
the PRICATCU50/8P selective hydration purifying of twice is crossed in embodiment 12 – recirculation c12/C13 alkene
In 600mLParr reactor, the PRICATCU50/8P (0.35 % by weight) of 300gC12/C13 raw material (by alumina column and molecular sieve purification, the C12 of 93.4%, the C13 of 4.4%) and reacted twice of 1.05g is used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.Blend sample is answered negate in 30 and 60 minutes.GC is used to monitor the disappearance of diene (C12:2 and C13:2) and the formation of monoene (C12:1 and C13:1) and paraffinic hydrocarbons (C12:0 and C13:0).Reaction proceeded to 94.4% transformation efficiency in 60 minutes, had 99.5% selectivity to cholesterol olefin product.Reaction mixture is carried out gravity filtration and collects limpid product.
embodiment 13 – PRICATCU50/8P selective hydration C13 alkene
In 600mLParr reactor, 300gC13 raw material (C13 of 90.6%) and 3.10gPRICATCU50/8P (1.0 % by weight) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.At 30,60,90,120,180 and 240 minutes acquisition reaction mixture samples.Use the disappearance of C13:2 alkene and both the formation of C13:0 and C13:1 alkene of GC monitoring reaction.Reaction proceeded to 27.3% transformation efficiency in 2 hours, had 99.6% selectivity to C13:1.Reaction is carried out gravity filtration and collected limpid product.
The C13 alkene that embodiment 14 – is purified with PRICATCU50/8P selective hydration
In 600mLParr reactor, 300gC13 raw material (by alumina column and molecular sieve purification, the C13 of 90.6%) and 3.04gPRICATCU50/8P (1.0 % by weight) are used N 2, then H 2purge each 15 minutes, then at 180 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure: reactor is recharged to 100psig when it is down to 50psig.Blend sample is answered negate in 30,60,90,120,150,180 and 210 minutes.Use the disappearance of C13:2 alkene and both the formation of C13:0 and C13:1 alkene of GC monitoring reaction.Reaction proceeded to 96.8% transformation efficiency in 2 hours, had 91.9% selectivity to C13:1.Reaction is carried out gravity filtration and collected limpid product.
the C13 alkene that embodiment 15 – is purified with PRICAT9908 selective hydration
In 600mLParr reactor, 300gC13 raw material (by alumina column and molecular sieve purification, the C13 of 90.6%) and 0.29gPRICAT9908 (0.1 % by weight, deglycerizin three ester before reaction) are used N 2, then H 2purge each 15 minutes.Then make these at 150 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure, and when it is down to 50psig, reactor is recharged to 100psig.Blend sample is answered negate in 30,60 and 90 minutes.Use the disappearance of C13:2 alkene and both the formation of C13:0 and C13:1 alkene of GC monitoring reaction.Reaction proceeded to 98.6% transformation efficiency in 60 minutes, had 94.9% selectivity to cholesterol olefin product.Reaction is carried out gravity filtration and collected limpid product.
the C15-C18 alkene that embodiment 16 – is purified with PRICATCU50/8P selective hydration
In 600mLParr reactor, by 300gC15-18 raw material (by alumina column and molecular sieve purification, the C15 of 50.6%, the C16 of 3.8%, the C17 of 1.4%, the C18 of 23.6%) and 0.30gPRICATCU50/8P (0.1 % by weight) use N 2, then H 2purge each 15 minutes.Then make these at 150 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure, and when it is down to 50psig, reactor is recharged to 100psig.Blend sample is answered negate in 30,60,90,120,150 and 180 minutes.Use the disappearance of diene (C15:2, C16:2, C17:2 and C18:2) and both the formation of saturates (C15:0, C16:0, C17:0 and C18:0) and monoene (C15:1, C16:1, C17:1 and C18:1) of GC monitoring reaction.Reaction proceeded to 86.7% transformation efficiency in 90 minutes, had 99.5% selectivity to cholesterol olefin product.Reaction is carried out gravity filtration and collected limpid product.
the C18 alkene that embodiment 17 – is purified with PRICATCU50/8P selective hydration
In 600mLParr reactor, 300gC18 raw material (by alumina column and molecular sieve purification, the C18 of 98.7%) and 0.31gPRICATCU50/8P (0.1 % by weight) are used N 2, then H 2purge each 15 minutes.Then make these at 180 DEG C, 100psigH 2lower reaction is stirred with the 100rpm of gas dispersion impeller.Monitoring H 2pressure, and when it is down to 50psig, reactor is recharged to 100psig.Response sample is got at 15,30 and 45 minutes.Use the disappearance of C18:2 alkene and both the formation of C18:0 and C18:1 alkene of GC monitoring reaction.Reaction proceeded to 93.8% transformation efficiency in 45 minutes, had 99.4% selectivity to C18:1.This is on the time period of 45 minutes.Gravity filtration is carried out in reaction, and collects limpid product.
the C18 alkene that embodiment 18 – is purified with PRICAT9908 selective hydration
In 600mLParr reactor, 300gC18 raw material (by alumina column and molecular sieve purification, the C18 of 98.7%) and 0.07gPRICAT9908 (0.02 % by weight, deglycerizin three ester before reaction) are used N 2, then H 2purge each 15 minutes.Then make it at 160 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2pressure, and when pressure reaches 50psig, reactor is recharged to 100psig.At 30,60,90 and 120 minutes acquisition reaction mixture samples.Use the disappearance of C18:2 alkene and both the formation of C18:0 and C18:1 alkene of GC monitoring reaction.Reaction proceeded to 51.3% transformation efficiency in 30 minutes, had 97.3% selectivity to C18:1.Reaction is carried out gravity filtration and collected limpid product.
embodiment 19-PRICAT9908 selective hydration C13FAME
In 600mLParr reactor, 300gC13FAME (C13 of 94%) and 0.7442gPricat9908 (0.25wt%, deglycerizin three ester before reaction) is used N 2, then H 2purge each 15 minutes, then at 150 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2reactor also recharges to 100psig when it is down to 50psig by pressure.30 minutes, 1h, 2h, 3h and 4h negate answers blend sample, and by the disappearance of C13:2FAME of GC monitoring reaction and the formation of C13:1 and 13:0FAME.Reaction reached completing of >99% in 3 hours, had 96% selectivity to C13:1.Reaction mixture is carried out gravity filtration and collects limpid product.
embodiment 20-PRICATCU50/8P selective hydration C13FAME
In 600mLParr reactor, 300gC13FAME (C13 of 94%) and 3.009gPricatCu50/8P (1.0wt%) is used N 2, then H 2purge each 15 minutes, then at 170 DEG C, 300psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2reactor also recharges to 100psig when it is down to 50psig by pressure.30 minutes, 1h, 2h, 3h, 4h and 5h negate answer blend sample and by GC monitoring reaction the disappearance of C13:2FAME and the formation of C13:1 and 13:0FAME.Reaction reached completing of >38% in 5 hours, had 98% selectivity to C13:1.Reaction mixture is carried out gravity filtration and collects the limpid product of blue/green.Product is containing the Cu of the 300ppm that has an appointment, and it leaches from catalyzer (leaching).
embodiment 21 – is by alumina column purifying C13FAME raw material
By PV and KarlFisher analyzing purity C13FAME raw material, there is the H of PV and 330ppm of 37.25meq/kg 2o content.In order to purification of samples, by raw material by activated alumina column, then at N 2under atmosphere on 4A molecular sieve dried overnight.PV is reduced to 2.17meq/mg and water is reduced to 118ppm.
embodiment 22-PRICAT9908 selective hydration C15FAME
In 600mLParr reactor, by 300gC15 raw material (by alumina column and molecular sieve purification, the C15 of >94%, the C15:2 of 34.7%) and 0.30gPricat9908 (0.1 % by weight, deglycerizin three ester before reaction) use N 2, then H 2purge each 15 minutes, then at 150 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2reactor also recharges to 100psig when it is down to 50psig by pressure.30 minutes, 1h, 2h, 3h and 4h negate answers blend sample, and by the disappearance of C15:2FAME of GC monitoring reaction and the formation of C15:1 and 15:0FAME.Reaction reached completing of >87% in 3 hours, had 81% selectivity to C13:1.Reaction mixture is carried out gravity filtration and collects limpid product.
embodiment 23-PRICAT9908 selective hydration C13-15FAME
In 600mLParr reactor, 300.46gC13FAME (C13 of 15%, the C14 of 21%, the C15 of 64%) and 0.2980gPricat9908 (0.10 % by weight, deglycerizin three ester before reaction) is used N 2, then H 2purge each 15 minutes, then at 150 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2reactor also recharges to 100psig when it is down to 50psig by pressure.Blend sample is answered and the disappearance of many unsaturated ester of being reacted by GC monitoring and the formation of cholesterol ester and unsaturated ester negate in 30,60,90 and 120 minutes.Reaction reached 88.5% complete in 3 hours, had 95% selectivity to cholesterol ester.Reaction mixture is carried out gravity filtration and collects limpid product.
the metathetic soybean oil of embodiment 24-PRICAT9908 diene-selective hydration
In 600mLParr reactor, 325.4gMSBO and 0.6541gPricat9908 (0.2 % by weight, deglycerizin three ester before reaction) is used N 2, then H 2purge each 15 minutes, then at 150 DEG C, 100psigH 2lower reaction is stirred with the 1000rpm of gas dispersion impeller.Monitoring H 2reactor also recharges to 100psig when it is down to 50psig by pressure.Blend sample is answered negate in 15,30,45,60 and 75 minutes.Sample and methyl alcohol carry out transesterify, and monitor the disappearance of C18:2 ester and the formation of C18:1 ester of reaction by GC.Reaction mixture is carried out vacuum filtration, and collects product (DSHMSBO).
the metathetic soybean oil of embodiment 25 – (MSBO) and diene-selective hydration greatly metathetic the oxidation-stabilized Journal of Sex Research of soya-bean oil (DSHMSBO)
18.0gMSBO or PHMSBO is added in a series of 20mL scintillation vial.By each material sample N 2purge 5 minutes, then in sealed tube at N 2store under atmosphere.Each material sample is stored in air atmosphere in sealed tube, and by last group sample storage in the pipe communicated with air.At 0,11,18 and 25 day, the PV of test sample was with the oxidative stability of research material.After 25 days, place the PV that the MSBO sample communicated with air has 46.2meq/kg, and the equivalent sample of DSHMSBO has the PV of 2.2meq/kg.
Brief overview from the observation of above-described embodiment is provided in the following table in 1 and 2.
Table 1
Table 2
1transformation efficiency is defined as (the total many unsaturatess in the total many unsaturates/raw materials in the total many unsaturates-products in raw material)
2selectivity is defined as (the total saturates in the total cholesterol thing+product in the total cholesterol thing/product in product)
3catalyzer recirculation before use once
4catalyzer recirculation before use twice
5the transformation efficiency of DSHMSBO changes into C18:1 and C18:0 as C18:2 and measures
Unless otherwise described, when analyzing the ester composition in previous embodiment, following analytical procedure described below is used:
Volatile products are analyzed by vapor-phase chromatography and flame ionization detector (FID).Fatty acid methyl ester (FAME) analysis uses Agilent6890 instrument and condition to carry out, and includes, but not limited to following methods:
Method 1: post: RestekRtx-wax, carbowax12438-6850,30mx250umx0.50um thickness
Injector temperature: 250 DEG C
Detector temperature: 300 DEG C
Furnace temperature: start temperature 100 DEG C, hold time 2 minutes, temperature rise rate 5 DEG C/min to 240 DEG C, 35 minutes working times
Carrier gas: hydrogen
Average gas velocity: 33cm/ second
Splitting ratio: 150:1
Method 2: post: RestekRtx-wax, carbowax12438-6850,30mx250umx0.50um thickness
Injector temperature: 250 DEG C
Detector temperature: 300 DEG C
Furnace temperature: start temperature 70 C, hold time 1 minute, temperature rise rate 20 DEG C/min to 180 DEG C, temperature rise rate 1.5 DEG C/min 240 DEG C, holds time 3.5 minutes, 50 minutes working times
Carrier gas: hydrogen
Average gas velocity: 54cm/ second
Splitting ratio: 150:1
Method 3: post: RestekRtx-wax, carbowax12438-6850,30mx250umx0.50um thickness
Injector temperature: 250 DEG C
Detector temperature: 300 DEG C
Furnace temperature: start temperature 70 C, hold time 1 minute, temperature rise rate 20 DEG C/min to 180 DEG C, holds time 0 minute, and temperature rise rate 3 DEG C/min to 240 DEG C, holds time 3.5 minutes, 30 minutes working times
Carrier gas: hydrogen
Average gas velocity: 54cm/ second
Splitting ratio: 150:1
Unless otherwise described, when analyzing the compositions of olefines in previous embodiment, following analytical procedure described below is used:
Volatile products are analyzed by vapor-phase chromatography and flame ionization detector (FID).Alkene analysis uses Agilent6890 instrument and condition to carry out, and includes, but not limited to following methods:
Method 1: post: RestekRtx-wax, carbowax12438-6850,30mx250umx0.50um thickness
Injector temperature: 250 DEG C
Detector temperature: 300 DEG C
Furnace temperature: start temperature 40 DEG C, hold time 5 minutes, temperature rise rate 10 DEG C/min to 240 DEG C, 25 minutes working times
Carrier gas: hydrogen
Average gas velocity: 29cm/ second
Splitting ratio: 150:1
Method 2: post: RestekRtx-wax, carbowax12438-6850,30mx250umx0.50um thickness
Injector temperature: 250 DEG C
Detector temperature: 300 DEG C
Furnace temperature: start temperature 70 C, hold time 5 minutes, temperature rise rate 5 DEG C/min to 240 DEG C, holds time 5 minutes, 44 minutes working times
Carrier gas: hydrogen
Average gas velocity: 31cm/ second
Splitting ratio: 150:1
Product by by peak and known standard substance, to compare together with the supported data from mass spectroscopy (GCMS-Agilent5973N) and characterize.
Post: Crossbond65% biphenyl, 30mx250umx0.1um
Injector temperature: 275 DEG C
Detector temperature: 375 DEG C
Furnace temperature: start temperature 40 DEG C, hold time 5 minutes, temperature rise rate 20 DEG C/min to 350 DEG C, holds time 31.5 minutes, 60 minutes working times
Carrier gas: helium
V-bar: 51.282cm/ second
Splitting ratio: 20:1
the biodegradability test of the partially hydrogenated C15-C18 alkene of embodiment 26 –
Obtain C15-C18 olefin samples, wherein the representative of sample intention is by the comparatively heavy olefin material of the biological concise generation of palmityl.Sample contain the C15 material of 56.6 % by weight, the C16 material of 3.4 % by weight and 38.3 % by weight C18 material.Many unsaturated olefins account for 21.7 % by weight of alkene in sample.The further details of sample is shown in following table 3.Use following catalyzer by sample part ground hydrogenation: 0.2%PRICAT9908 nickel catalyzator.Partial hydrogenation is at the H of 100psi 2occur under pressure, and in the hydrogenation reactor being equipped with 1000rpm gas dispersion impeller, carry out 35 minutes at 140 DEG C.N is carried out before reaction 2purge, H subsequently 2purge.Once react, then collect the C15-C18 olefin samples with part of detecting hydrogenation.The result of testing after hydrogenation is shown in Table 3.
Before the hydrogenation and afterwards test organisms degraded.Use Closed-BottleBiodegradationTest, ModifiedISO11734:1995, EPA-821-R-11-004, AnalyticMethodsfortheOilandGasExtractionPointSourceCateg ory, Method1647 test the biological degradation of each olefin samples.Toxicity appraisal is carried out: the AppendixA of LeptocheirusplumulosusAcute, Static10-daySedimentToxicityTest, ASTMTestNo.E1367-99 and GMG290000 according to following.Use the unhydrided sample of alumina filter and partially hydrogenated sample before test.
table 3
* TGP is Theoretical gas generation calculated value (TestMethod1647, EPA-821-R-11-004) being produced the clean average gas generation corrected by the average gas of blanket depositions control sample
Above-described embodiment collectively illustrates the key step described in process program, show and manufacture alkene, paraffinic hydrocarbons, metathetic triglyceride level, unsaturated fatty acid ester and acid and diacid compounds from natural oil, it can be used as chemical, solvent and fuel blended material, such as, as the drilling fluid for petroleum prospecting.

Claims (33)

1. the method for refining natural oil, comprising:
The raw material comprising natural oil is provided;
Make raw material in double decomposition reactor, under the existence of metathesis catalyst, react to be formed the metathesis product comprising many unsaturated olefins and many unsaturated ester; With
Make the partly hydrogenation in the presence of a hydrogenation catalyst of many unsaturated olefins and/or many unsaturated ester, wherein many unsaturated olefins and/or many unsaturated ester are converted into cholesterol alkene and/or cholesterol ester at least partially.
2. the method for claim 1, is separated the many unsaturated olefins in metathesis product from the many unsaturated ester metathesis product before being included in step of hydrogenation further.
3. the method for claim 2, wherein many unsaturated olefins are converted into cholesterol alkene at least partially.
4. the method for claim 3, wherein step of hydrogenation has the transformation efficiency of at least 85% and the selectivity of at least 90%.
5. the method for claim 3, wherein step of hydrogenation has the transformation efficiency of at least 90% and the selectivity of at least 95%.
6. the method for claim 3, wherein step of hydrogenation has the transformation efficiency of at least 95% and the selectivity of at least 99%.
7. the method for claim 2, after the separation step and before step of hydrogenation, carries out transesterify in the presence of an alcohol to form ester exchange offspring by many unsaturated ester.
8. the method for claim 2, after separating step and step of hydrogenation, carries out transesterify in the presence of an alcohol to form ester exchange offspring by cholesterol ester.
9. the method for claim 2, wherein many unsaturated olefins are converted into cholesterol ester at least partially.
10. the method for claim 9, wherein step of hydrogenation has the transformation efficiency of at least 85% and the selectivity of at least 90%.
The method of 11. claims 9, wherein step of hydrogenation has the transformation efficiency of at least 90% and the selectivity of at least 95%.
The method of 12. claims 9, wherein step of hydrogenation has the transformation efficiency of at least 95% and the selectivity of at least 99%.
The method of 13. claims 2, wherein many unsaturated olefins are converted into cholesterol alkene and many unsaturated ester are converted into cholesterol ester at least partially at least partially.
14. the process of claim 1 wherein that hydrogenation catalyst comprises the metal being selected from nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium and combination thereof.
15. the process of claim 1 wherein that hydrogenation catalyst provides with the amount of the 0.01-1.0 % by weight of many unsaturated olefins and/or many unsaturated ester.
16. the process of claim 1 wherein that step of hydrogenation carries out 30-180 minute with the hydrogen pressure of 50psig-500psig at the temperature of 150 DEG C-250 DEG C.
17. the process of claim 1 wherein hydrogenation catalyst recirculation before step of hydrogenation.
The method of 18. claims 1, is included in further and makes before raw material reacts under the existence of metathesis catalyst, under the condition being enough to the catalyzer poison reduced in raw material, to process raw material,
Wherein with one or more following process raw materials: heat, molecular sieve, aluminum oxide, silica gel, illiteracy unsticking soil, Fuller's earth, bleaching clay, diatomite, zeolite, kaolin, activated metal, acid anhydrides, gac, SODA ASH LIGHT 99.2, metal hydride, metal sulfate, metal halide, metal carbonate, metal silicate, Vanadium Pentoxide in FLAKES, metal alanates, alkyl aluminum hydride, metal borohydride, organometallic reagent and carbon-containing palladium catalyst.
The method of 19. claims 18, wherein raw material through chemical reaction carries out chemical treatment to reduce catalyzer poison, and wherein chemical reaction relates to one or more following process raw materials: metal hydride, metal sulfate, metal halide, metal carbonate, metal silicate, Vanadium Pentoxide in FLAKES, metal alanates, alkyl aluminum hydride, metal borohydride and organometallic reagent.
The method of 20. claims 18, is not wherein depositing the temperature that is heated in the case of oxygen be greater than 100 DEG C by raw material and is keeping time of being enough to reduce catalyzer poison at such a temperature.
The method of 21. claims 1, comprises further and provides low molecular weight olefins or middle-molecular-weihydroxyethyl alkene, and wherein reactions steps comprises the cross-metathesis between raw material and low molecular weight olefins or middle-molecular-weihydroxyethyl alkene.
The method of 22. formation cholesterol alkene, comprising:
The raw material comprising many unsaturated olefins is provided; With
Make many unsaturated olefins at the temperature of 150 DEG C-250 DEG C, use the hydrogen pressure partly hydrogenation 30-180 minute of 50psig-500psig in the presence of a hydrogenation catalyst,
Wherein hydrogenation catalyst provides with the amount of the 0.01-1.0 % by weight of many unsaturated olefins, and wherein step of hydrogenation has the transformation efficiency of at least 85% and the selectivity of at least 90%.
The method of 23. claims 22, wherein processed raw material before step of hydrogenation under the condition being enough to the catalyzer poison reduced in raw material,
Wherein with one or more following process raw materials: heat, molecular sieve, aluminum oxide, silica gel, illiteracy unsticking soil, Fuller's earth, bleaching clay, diatomite, zeolite, kaolin, activated metal, acid anhydrides, gac, SODA ASH LIGHT 99.2, metal hydride, metal sulfate, metal halide, metal carbonate, metal silicate, Vanadium Pentoxide in FLAKES, metal alanates, alkyl aluminum hydride, metal borohydride, organometallic reagent and carbon-containing palladium catalyst.
The method of 24. claims 22, wherein hydrogenation catalyst comprises the metal being selected from nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium and combination thereof.
The method of 25. claims 22, wherein transformation efficiency is at least 90% and selectivity is at least 95%.
The method of 26. claims 22, wherein transformation efficiency is at least 95% and selectivity is at least 99%.
The method of 27. claims 22, wherein hydrogenation catalyst recirculation before step of hydrogenation.
The method of 28. formation cholesterol esters, comprising:
The raw material comprising many unsaturated ester is provided; With
Make many unsaturated ester at the temperature of 150 DEG C-250 DEG C, use the hydrogen pressure partly hydrogenation 30-180 minute of 50psig-500psig in the presence of a hydrogenation catalyst,
Wherein hydrogenation catalyst provides with the amount of the 0.01-1.0 % by weight of many unsaturated ester, and wherein step of hydrogenation has the transformation efficiency of at least 85% and the selectivity of at least 90%.
The method of 29. claims 28, wherein processed raw material before step of hydrogenation under the condition being enough to the catalyzer poison reduced in raw material,
Wherein with one or more following process raw materials: heat, molecular sieve, aluminum oxide, silica gel, illiteracy unsticking soil, Fuller's earth, bleaching clay, diatomite, zeolite, kaolin, activated metal, acid anhydrides, gac, SODA ASH LIGHT 99.2, metal hydride, metal sulfate, metal halide, metal carbonate, metal silicate, Vanadium Pentoxide in FLAKES, metal alanates, alkyl aluminum hydride, metal borohydride, organometallic reagent and carbon-containing palladium catalyst.
The method of 30. claims 28, wherein hydrogenation catalyst comprises the metal being selected from nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium and combination thereof.
The method of 31. claims 28, wherein transformation efficiency is at least 90% and selectivity is at least 95%.
The method of 32. claims 28, wherein transformation efficiency is at least 95% and selectivity is at least 99%.
The method of 33. claims 28, wherein hydrogenation catalyst recirculation before step of hydrogenation.
CN201480015348.6A 2013-03-14 2014-03-11 Diene-selective hydrogenation of metathesis-derived olefins and unsaturated esters Pending CN105189722A (en)

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