CA2073178A1 - Process for the preparation of octenes - Google Patents
Process for the preparation of octenesInfo
- Publication number
- CA2073178A1 CA2073178A1 CA002073178A CA2073178A CA2073178A1 CA 2073178 A1 CA2073178 A1 CA 2073178A1 CA 002073178 A CA002073178 A CA 002073178A CA 2073178 A CA2073178 A CA 2073178A CA 2073178 A1 CA2073178 A1 CA 2073178A1
- Authority
- CA
- Canada
- Prior art keywords
- butene
- weight
- catalyst
- process according
- per cent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/10—Catalytic processes with metal oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A mixture of isomeric octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule is prepared by dimerizing of n-butene by contact with a nickel oxide catalyst on a silica-alumina support at a temperature above 150 ·C at a liquid hourly weight feed rate from 0.4 to 1.8 h-1.
Description
PROCESS FOR THE PREPAR~I~Q~ OF OCT~
This invention relates to the production of oc~enes by dimerizing of butenes.
Octenes are useful for conversion by the oxo alcohol process into the correspondinq nonyl alcohols which are used inter ~li~ in the manufacture of plasticissrs, lubricating oil additives, detergents and defoamers. For this purpose, mixtures of isomeric octenes are customarily used but it is important that the mixture shall contain a blend of isomers giving rise to the desired properties in the final product.
It is convenient to measure the proportions of the various isomers which are present by giving the average number of side chain methyl groups per molecule in the mixture. n-Octenes, for example, contain no side chain methyl groups, methyl-heptenes contain l side chain methyl group; dimethyl-- 15 hexenes contain 2 side chain methyl groups; and trimethyl-pentenes contain 3 side chain methyl groups. A mixture of isomeric octenes having an average of l.6 to 2.0 side chain methyl groups per molecule-is widely regarded as especially suitable for conversion into nonyl alcohols for use in plasticisers.
It is known to dimerize olefins by contact with a nickel oxide catalyst at elevated temperature. ~or example, United States Patent No. 3649710 (Neal et al) describes a process in which butene and propylene are first pre-treated and then co-dimerized by passing over a nickel oxide PCT/GB90/020t1 catalyst. It i5 said that the pre-treatment of the olefin feed substantially improves the life of the catalyst. The co-dimerizing is effective at a temperature in the range of 175 to 250-F under pressur-s of 30 to 50 atmospheres. The advantage of the process is stated to be that the processing tec~niques described produce an acceptable butene feQd free of catalyst poisons which would rapidly deactivate the catalyst if not removed. United State~ PatQnt ~o. 3658935 (Pine) describes a process for dimerising or co-dimerising an impure feed ~ixture containing n-butene propylene or mixtures thereof contaminated with impurities by passage over a nickel oxide catalyst. Hydrogen is added to the feed to lengthen the life of the nickel oxide catalyst and improve the proportion of desired dimers in the product. The co-15 dimerizing is conducted at 140 to 300-F under a pressure from about 150 psi to 1000 psi. These references illustrate that it has long been known that nickel oxide catalysts used in the dimerizing of olefins are liable to be deactivated by poisons present in the olefin feed.
British Specification No. 1069296 discloses the production of dimers from olefins such as butene by contact with a catalyst containing aluminum and nic~el ions on a silica support at temperatures up to 400-C. British Specification No. 1215943 discloses the dimerizing of olefins including butenes by contact with the 6ame ~ind of catalyst which is activated in a slightly different manner. The WO91/09826 PCT/GB90/020t1 -3- 207~178 c~talyst used in these ~pecifications differs from those used in the two United States Patents referred to above, and in the present invention, by including only a small proportion of nic~el and aluminum.
East German Specification No. 1060037 describes inter the dimerizing of a mixture of butenes over a catalyst based on amorphous alumina ~ilicate containing a small proportion of nic~el oxide. The Dperating temperature was only about lOO-C, but temperatures as high as 180-C are disclosed with other olefin starting materials.
Such known methods for dimerising butene to octenes suffer from one or more disadvantages, e.g. the blend of isomeric octenes obtained does not give the desired properties in the nonyl alcohols or their derivatives; the total conversion of butene into octene per pass over the catalyst used is too low le.g. less than 50 per cent); and the nickel oxide catalyst is susceptible to the presence of poisons 6uch as oxygenated compounds or organic ~ulphur and nitrogen compounds, in the butene feed. Such poisons are often difficult to avoid unless expensive purification procedures are used.
The present invention provides an improved process for the production of a mixture of isomeric octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule.
The new process gives a high conversion rate per pass. While it can be operated with pure or ~ubstantially pure butene 20731 78 ~4~
feed, it can also be used with feQds of typical commercial purity and, with only slight modification, with reeds ~ontaining appreciable amounts of sulphur-containing catalyst poisons.
According to the present invention, n mixture of isomeric octenes having an average of l.6 to 2.0 side chain methyl groups per molecule and containing not more than 8 per cent by weight of octenes having 3 side chain methyl groups per molecule is made by a process which comprises contacting an n-butene, for example in the form of a mixture containing at least 20 per cent by weight of an isomeric mixture of n-butenes and not more than 80 per cent by weight of saturated hydrocarbons, and preferably not more than l.5 per cent by weight of isobutene, at a temperature between about 150-C and 275-C and in the supercritical state with a nicXel oxide (Nio) catalyst containing 5 to 30 per cent by weight, preferably 20 to 30 per cent by weight, of NiO on a silica-alumina support containing l0 to 45 per cent by weight of Al2O3 and having at least a surface area of l00 m2/g, preferably between l00 to 450 m2/g at a liquid hourly weight feed rate of the said butene over the said catalyst being 0.4 to l.8 h-l, preferably between 0.6 and 0.7 h-l.
It has been found that by operating under conditions such that the butene is contacted with the catalyst at a temperature above 150 C, the possible presence of oxygen or nitrogen containing compounds in the butene feed does not affect the activity or life of the catalyst. Moreover, the WO 91/09826 PCI'/GB90/02011 conversion rate is not affected and the ~electlvity of the process for the desired octene mixture i~ not ~ub~tant$ally affected.
For example if an n-butene feed containing 9iO ppmw of t-butyl alcohol and 250 ppmw of ~ater i~ dimerizQd at 80 to lOO-C, the catalyst only has a life of le68 than 3 days corre~ponding to a weight ratio of product to cataly~t of up to about 20. Under the conditions of the pre~ent invention, however, using the said feed and catalyst, the weight ratio of product to catalyst rises to over 600.
The catalyst can tolerate, under the specified operating conditions, the presence of small a~ounts of sulphur-containing compounds, such as organic sulphides or thiophenes, e.g. 1 to 40 ppmw, and preferably less than 20 or ` 15 more preferably less than 10 ppmw in the butene feed without substantial deactivation over 6everal days of operation.
Surprisingly, however, it has been found that the new process can be operated even with butene feeds containing larger amounts of sulphur provided that a small amount of a nitrogen-containing compound is present in, or is Added to, the feed. The presence of ~uch nitrogen-containing compound apparently prevents the sulphur in the feed from binding to the nickel oxide and deactivating it. According, therefore, to a feature of the invention, when the butene feed contains from 20 to 200 ppm, especially 20 to 40 ppm, of sulphur, the effect of such sulphur is counteracted by adding to the .
, ,, ~ . . .
;
207317~ -6-butene feed from 50 to 2000 ppm of a nitrogen-containing organic compound.
n-Butenes suitable for use in the present invention are commercially available from petroleum refinery operations. As already noted, such butenes should not contain more than l.5~ of isobutenes, because isobutene tends to ~orm products with a high degree of branching. Preferably the butenes consist substantially entirely oS l-butene, cis-2-butene and/or trans-2-butene. The presence of fully saturated hydrocarbons in the feed is not in general detrimental, but if the proportion rises above about 80 per cent by weight the process becomes uneconomic. The presence of olefins containing more than 4 carbon atoms per molecule should likewise be avoided because they reduce the selectivity of the reaction to produce octenes.
The nickel oxide on silica-alumina catalyst used in the present invention is known and has been described in, for example, United States Patent 2581228. It may be made by treating a calcined silica-alumina gel with a solution of a water-soluble nickel salt, and then with an agent to precipitate the nickel on the gel, e.g. as the hydroxide or carbonate. The silica-alumina gel with the nickel hydroxide or carbonate precipitated thereon is then filtered off and dried and calcined. The proportion of Nio is chosen to provide essentially what is equivalent to a monolayer of the Nio on the silica-alumina support. Smaller or larger amounts of Nio reduce W091/09826 PCT/GB~/02011 207~
catalyst actlvlty. The proportion of alumina i8 chosen to provide a high conver6ion rate combined with acceptable catalyst life. Too little alumina allows rapid catalyst deactivation, while too much qives poor conversion rates. It has been found that the tomperature of the calcination not only affects catalyst life but also can dramatically affect the isomer distribution in the mixture of octenes obtained in the new process. Preferably the catalyst is calcined at S00 to 700C so that a ~ixture containing a large proportion of octenes having an average of l.6 to 2.0 side chain methyl groups per molecule is obtained.
The reaction temperature must be at least 150 C in order to achieve the required conversion rate and average number of methyl groups per molecule. However, if the lS temperature is too high, the proportion of side chain methyl groups increase, and it is therefore desirable to use a reaction temperature below about 275 C. Preferably, the contact temperature is in the range of 175 to 225 C, and it is especially preferred to operate at a temperature in the range of 180 to 200 C. The pressure in the reaction zone must be sufficient to keep the butenes in the supercritical state at the operating temperature. In practice this requires a pressure in the range of about 50 to 200 bars, preferably about 70 bars.
As already indicated, the feed rate of the octene mixture should be such as to ensure a liquid hourly weight 2 ~ 7 317 8 -8-feed rate from o.4 to l.8, preferably 0.6 to 0.7 h-l. Above this feed rate the butene conversion falls to unacceptable levels and the number of side chain methyl groups per octene ~olecule fallc below l.6.
As already noted, when the butene feed contains ~ore than about 5 ppm of sulphur, derived from mercaptans, disulphides, hydrogen sulphide and the like, the poisoning effect of the sulphur can be counteracted by adding to tbe feed from S0 to 2,000 ppm of a nitrogen-containing compound.
Suitable nitrogen-containing compounds are aliphatic and saturated heterocyclic primary, secondary and tertiary amines containing l to 12 carbon atoms, e.g. mono-, di- or tri-ethyl- amine or a saturated heterocyclic amine such as pyrrollidine. It is believed that such nitrogen-containing lS compounds are effective because they prevent the sulphur-containing poisons in the butene feed from becoming bound to the nickel oxide catalyst and deactivating it. It is surprising that the nitrogen-containing compounds have this effect because at lower temperatures than those used in the present invention, such compounds are themselves regarded as catalyst poisons.
The process of the present invention does not require special apparatus and can be operated in any reactor configuration which is capable of promoting intimate contact between the butene feed and the cata~yst. The process can be operated batchwise, ~emi-batchwise, or continuously.
Continuous operation in a fixed bed reactor is preSerred.
WO 91/09826 PCI'/GB90/02011 9 .
Besides the desired octene mixture, the process of t~e present invention produces minor amounts of C5_7 and Cg_ 16 olefins. Of these the most important are the dodecenes, which in some cases are produced in a weight proportion as high as half that of the octenes. It is usually economically worthwhile to isolate and separate such by-product olefins.
The following Examples illustrate the invention:
Examples ~-24 The butene feed in these Examples was a commercial product which contained the following major ingredients and impurities:
EE~ IMPlJ~ IES
iso-butane : 4.3 wt% 1,3-butadiene : 350 ppmw n-butane : 14.5 acetylenics : ~10 ppmw 15 n-butene-l : 44.5 oxygenates (alcohols) : C 5 ppmw iso-butene : 1.2 ethers : < 5 ppmw trans-butene-2 : 22.0 sulfur : 2 ppmw cis-butene-2 : 13.5 chlorine : < 2 ppmw The butene mixture was passed over a 28 weight per cent Nio catalyst on a silica-alumina support containing 75 weight per cent silica and 25 weight per cent alumina, in the form of 3 mm tablets at a temperature in the range 185 to 195 C at a liguid hourly weight feed rate of about 0.6 to 25 ~1.6. The pressure in the reaction zone was maintained at 70 bars.
In the Tables:
a) W.W.H. is the liguid hourly weight feed rate, in the case of the hatch examples 44-61 this is defined as the wosl/o9826 PCT/CB90/02011 3~ o-inverse of the feed weight divided by the catalyst weight multiplied by the reaction time.
b) CATLIFE, WprOd/Wcat~ is the length of each experimental run measured as the ratio of weight product produced to weight of catalyst used.
c) Conversion is the percentage of butene feedstock reacted.
d) Select~ity is the ratio of a specific product to the amount of butene feedstock reacted.
ej Yield is selectivity x conversion.
"ISOMER DISTRIBUTION" is C8 isomer distribution and "av Branchiness" is the average number of methyl groups per molecule obtained by gas chromatographic analysis of the octene product after hydrogenation.
The following Table shows the results of 24 experiments:
WO 91/09826 ~ PCI/GB90/02011 In ~In~ ON 2a73~78 t rl ~ o~ ~ ~ ~ ~ g r~
I~
N
S r. ~ S
~ ~ N N 0 ~ 8 r, ~; ~ N N _ ~ ~ I;i ~ o ~"
o ~ ~ ~ N ~ o ~ ~ In O ~
N ~ O H - ~ 8 1~ ~ O ~ ~ H
H ~ 1~ ~ N 0~ ~ O ~ O ~ o ~1 N ~ H ~ N o N r~ g ~5 ~i 0 H ~O o 1~ 0 ~ ~1 N ~ O ~i N H
~ ~ ~ m o ~
g 0 O 1~ ~ ~ t~ N ' g - N ~ ~~ ~ ~ N ~ ~ ~ H O
H ~ , H~r ~ t~ H o o ~
n ,~ ~ ~ N rl ~ ~ g 8 ~3 , , WO 91/09826 - 12 - PCI`/GB90/02011 o . ~ O ~ . r~ ~ r, ~; o ~ ~ o ~ , . ,~ I` ~ ~ O g N r~ ~ ~1 ~ ' ~ N
N ~; 1` ~ 0 6 . .
~S ~ '~ ~ ~ O O ~ ~ O n o o ~
o o ~ ~ o ~ O o C ~n r~
O~ N
o I ~ j 1~1 1 . ,,~ ,, .
-13- 2 ~7 3 17 8 ~E~amples 25 to 4~
The butene feed in these Examples contained the following major ingredients and impurities:
E~ =~
iso-butane : 3.3 wt% 1,3-butadiene :4850 ppmw n-butane : 36.8 acetylenics :50 ppmw n-butene~l 33.0 oxygenates (alcohols) : 30-50 ppmw iso-butene : 1.4 Me2O : 50 ppmw trans-butene-2 : 15.9 Et2S : 8 ppmw as S
cis-butene-2 : 9.6 Me25 : 7 ppmw as S
Cl : < 2 ppmw The mixture of n-butenes was contacted with the same catalyst as that used in Examples 1 to 24 (in the for~ of 3 mm tablets) at the temperatures, pressures and contact times shown in the following table:
WO 9t/09826 PCl/GB90/02011 201 3~ 1~
1'1 N 1~ ~ ~; N ~'~N O ~ O t~
.n a~ ~ ' '' . ~ N O
~ N ~` ~ $ 1~ o " ~ ~ ~ ~4 I~ N ~ N ~ ~ O ~-- ~ r~ I N
N O O o ~ ~,~ g g O O
,~ nO Ci ~jj N N I
o~ g r~ o In ~ O
O ~I h ~ ~ o ~ ~ N ~ N ~ ~ ~ j~ O t~ O ~0 r~ ~1 N ~ B N
~ ~ ~ S ~ O
x ~ ~ ., Il, ., ~ ~ o 3 ~ g ~ O H g ~ ~ N ~ ' N
~ ~ ' N ~ ~ ~ ~ N H o o o~
N ~ t` rl O O ~ ~ ~1 0 0 0 1~ rl ~i 5 ~ ~ 'NN ", ~ r~ g 11~ ~ O ,~Iti ,~ O N ~ n ~
~ 8 WO 91/09826 PCl'/GB90/02011 O " ~ o ~ O ~O ; ~
5 ~ . i ~ ;2 " a ~ n H H ~ ~ æ
~: o o o n ~ o~ N ~ 8 N ~ 1 O 0 ~ O ~ O t~ ~ 1 o~ ~3 o ~ ô 1~ rl N ~ 8 ,~ E ~ æ
~ H ~ ~ O O
O N t~ N 1~ 0 ~ ~ O 0 ~ ~ ~i ~ o o ~ o 3 ~ ~ N ~ N ~O O
N ~ ~ ~ ~ ~ O r~
N ~ ~i ~ N ~-~ O O N ; ' ' 207 3~7 8 -16-Exam~lçs 44 to 50 In a furt~er 6eries of experiments pure n-butene-l was contacted with the same nickeloxide on silica-alumina catalyst at temperatures in the range 155 to 220 C and at contact times from 0.67 to 1.67 per hour with the results shown in the following table:
T~L~ 3 Ex .No~ W.W.H. Temp.C Percent. Conv. Average CH3/mol 44 0.67 180 81 1.77 1045 0.67 125 75 1.50 46 1.00 200 81 1.71 47 0.67 220 81 1.65 48 1.67 220 77 1.72 49 1.67 155 78 1.61 1550 1.00 155 78 1.65 These results show that too low a temperature gives too low a proportion of side chain methyl per molecule.
Examples 51-57 The same procedure as in Examples 44 to 50 was repeated usinq trans-2-butene as the starting material. The catalyst (which was the same as that used in Example 1) was crushed to 10-14 mesh particles and then calcined in an electric furnace at 500-C for 16 hours in flowing air. In a dry box, a 300 ml autoclave was loaded with the catalyst, a known weight of decane used as internal standard, and (where acid) an additive ~pentanethiol, pyrrolidine, diethyl disulfide). ~he autoclave was evacuated/N2-purqed three times, then charged decane used as internal ~tandard, and (where acid) an additive (pentanethiol, pyrrolidine, diethyl disulfide). The autoclave was evacuated/N2-pur~ed t~ree times, then charged with a known amount of high purity (>99%) butQne. Thi~ atep was followed ~y heating the autoclavQ to the s~t t~mperature for predetermined length of time with continuous 6tirring.
The butene/catalyst weight ratio and heating time corresponded to the space velocity indicated in Tabl- 4 below. At the end of th- run, the autoclave was cooled to ~5-C, vented to the air, and the liquid product was analysed by gas chromatography. The following results were obtained:
WO 91/09826 PCI/C;B90/02011 c~ --18--'l 3 ~r~ ~ o s V
. . . . . . .
. _ _ _ , , _ , D
~ ~ I
V ~C ~, O ~ /
O Cl.
v ~J ~ o~
_ ~ ~C ~
~ ll _ U
Ql IC 11~ 0 _~ C ~ _~ _ ~ O ~ ~ h~ _ u~ ~ r ~ ~ 0 dO ~ ~0 U~ U
C D
I
~ C
_ V~
~J ~ U
C ~ O~
a~ ~ c ~ u U C o r~ _ o ~ ~ o~
o , a~ CD ~ I` ~ I` .
w ~. ~ O.V a~
.. :) C
~ V V-~l E~ CL u~ C U V
E ~) t~ r u~ u~ u ~ _, ~o _ _ _ _ _ _ _ v a~ v E~ ~ ~ c ~ V
:r . v ~c o o o o o o o . . . .
3 _ _ _ _ _ , _ ~ ~ c a~ o ~0 c c ~ ~ s ~
:~ ' :) ") ~ D ~
_~ --o --o --O V C .
v E _ o ~o _o ~ ~_~
o u~ o o o o s s ~ c I V V
3 c c ~ ~ ~ c ~ ~ O
~C zO zO ~ ~ zo z ~ vo Vc Ea' S~
O E S C S QJ ~ ~- ~
., --~ ~ _ ~. ~q v 0 3 C--I c _ c ~ E C
G ~ J ~ tO ~ ~ ~ S ~ t s _ ~Q. ~ ~ O
v v v al v :~ I~ v ~ t~a, u, o t~
~ C C C C ~ U~ .
oa~ ~ a) o ~-- ---,-~ v ~J S Q
ZP~ ~ Z ~ ~ ~ ~ S ~
K O ~ D 1` _ _C~ O
~ Z U~ 7 U
C
E~mples 58-61 The same procedure as in Examples 44 to S0 was repeated using pure trans-2-butene as the starting mater~al and the same catalyst as that u~ed in Examples 51-58. The temperature and feed rate was varied as shown in the following Table which also shows the results obtained.
Ex. ~o W.W.H Tem~.C percent.Conv. AveraGe CH3~2~L
58 1.00 175 83 1.62 ~9 5.00 175 58 1.43 ~0 l.OO 95 72 1.58 :
61 5.00 95 44 1.39 These results show that too high a feed rate or too low an operating temperature fail to achieve the desired degree of j branching of the octene product.
This invention relates to the production of oc~enes by dimerizing of butenes.
Octenes are useful for conversion by the oxo alcohol process into the correspondinq nonyl alcohols which are used inter ~li~ in the manufacture of plasticissrs, lubricating oil additives, detergents and defoamers. For this purpose, mixtures of isomeric octenes are customarily used but it is important that the mixture shall contain a blend of isomers giving rise to the desired properties in the final product.
It is convenient to measure the proportions of the various isomers which are present by giving the average number of side chain methyl groups per molecule in the mixture. n-Octenes, for example, contain no side chain methyl groups, methyl-heptenes contain l side chain methyl group; dimethyl-- 15 hexenes contain 2 side chain methyl groups; and trimethyl-pentenes contain 3 side chain methyl groups. A mixture of isomeric octenes having an average of l.6 to 2.0 side chain methyl groups per molecule-is widely regarded as especially suitable for conversion into nonyl alcohols for use in plasticisers.
It is known to dimerize olefins by contact with a nickel oxide catalyst at elevated temperature. ~or example, United States Patent No. 3649710 (Neal et al) describes a process in which butene and propylene are first pre-treated and then co-dimerized by passing over a nickel oxide PCT/GB90/020t1 catalyst. It i5 said that the pre-treatment of the olefin feed substantially improves the life of the catalyst. The co-dimerizing is effective at a temperature in the range of 175 to 250-F under pressur-s of 30 to 50 atmospheres. The advantage of the process is stated to be that the processing tec~niques described produce an acceptable butene feQd free of catalyst poisons which would rapidly deactivate the catalyst if not removed. United State~ PatQnt ~o. 3658935 (Pine) describes a process for dimerising or co-dimerising an impure feed ~ixture containing n-butene propylene or mixtures thereof contaminated with impurities by passage over a nickel oxide catalyst. Hydrogen is added to the feed to lengthen the life of the nickel oxide catalyst and improve the proportion of desired dimers in the product. The co-15 dimerizing is conducted at 140 to 300-F under a pressure from about 150 psi to 1000 psi. These references illustrate that it has long been known that nickel oxide catalysts used in the dimerizing of olefins are liable to be deactivated by poisons present in the olefin feed.
British Specification No. 1069296 discloses the production of dimers from olefins such as butene by contact with a catalyst containing aluminum and nic~el ions on a silica support at temperatures up to 400-C. British Specification No. 1215943 discloses the dimerizing of olefins including butenes by contact with the 6ame ~ind of catalyst which is activated in a slightly different manner. The WO91/09826 PCT/GB90/020t1 -3- 207~178 c~talyst used in these ~pecifications differs from those used in the two United States Patents referred to above, and in the present invention, by including only a small proportion of nic~el and aluminum.
East German Specification No. 1060037 describes inter the dimerizing of a mixture of butenes over a catalyst based on amorphous alumina ~ilicate containing a small proportion of nic~el oxide. The Dperating temperature was only about lOO-C, but temperatures as high as 180-C are disclosed with other olefin starting materials.
Such known methods for dimerising butene to octenes suffer from one or more disadvantages, e.g. the blend of isomeric octenes obtained does not give the desired properties in the nonyl alcohols or their derivatives; the total conversion of butene into octene per pass over the catalyst used is too low le.g. less than 50 per cent); and the nickel oxide catalyst is susceptible to the presence of poisons 6uch as oxygenated compounds or organic ~ulphur and nitrogen compounds, in the butene feed. Such poisons are often difficult to avoid unless expensive purification procedures are used.
The present invention provides an improved process for the production of a mixture of isomeric octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule.
The new process gives a high conversion rate per pass. While it can be operated with pure or ~ubstantially pure butene 20731 78 ~4~
feed, it can also be used with feQds of typical commercial purity and, with only slight modification, with reeds ~ontaining appreciable amounts of sulphur-containing catalyst poisons.
According to the present invention, n mixture of isomeric octenes having an average of l.6 to 2.0 side chain methyl groups per molecule and containing not more than 8 per cent by weight of octenes having 3 side chain methyl groups per molecule is made by a process which comprises contacting an n-butene, for example in the form of a mixture containing at least 20 per cent by weight of an isomeric mixture of n-butenes and not more than 80 per cent by weight of saturated hydrocarbons, and preferably not more than l.5 per cent by weight of isobutene, at a temperature between about 150-C and 275-C and in the supercritical state with a nicXel oxide (Nio) catalyst containing 5 to 30 per cent by weight, preferably 20 to 30 per cent by weight, of NiO on a silica-alumina support containing l0 to 45 per cent by weight of Al2O3 and having at least a surface area of l00 m2/g, preferably between l00 to 450 m2/g at a liquid hourly weight feed rate of the said butene over the said catalyst being 0.4 to l.8 h-l, preferably between 0.6 and 0.7 h-l.
It has been found that by operating under conditions such that the butene is contacted with the catalyst at a temperature above 150 C, the possible presence of oxygen or nitrogen containing compounds in the butene feed does not affect the activity or life of the catalyst. Moreover, the WO 91/09826 PCI'/GB90/02011 conversion rate is not affected and the ~electlvity of the process for the desired octene mixture i~ not ~ub~tant$ally affected.
For example if an n-butene feed containing 9iO ppmw of t-butyl alcohol and 250 ppmw of ~ater i~ dimerizQd at 80 to lOO-C, the catalyst only has a life of le68 than 3 days corre~ponding to a weight ratio of product to cataly~t of up to about 20. Under the conditions of the pre~ent invention, however, using the said feed and catalyst, the weight ratio of product to catalyst rises to over 600.
The catalyst can tolerate, under the specified operating conditions, the presence of small a~ounts of sulphur-containing compounds, such as organic sulphides or thiophenes, e.g. 1 to 40 ppmw, and preferably less than 20 or ` 15 more preferably less than 10 ppmw in the butene feed without substantial deactivation over 6everal days of operation.
Surprisingly, however, it has been found that the new process can be operated even with butene feeds containing larger amounts of sulphur provided that a small amount of a nitrogen-containing compound is present in, or is Added to, the feed. The presence of ~uch nitrogen-containing compound apparently prevents the sulphur in the feed from binding to the nickel oxide and deactivating it. According, therefore, to a feature of the invention, when the butene feed contains from 20 to 200 ppm, especially 20 to 40 ppm, of sulphur, the effect of such sulphur is counteracted by adding to the .
, ,, ~ . . .
;
207317~ -6-butene feed from 50 to 2000 ppm of a nitrogen-containing organic compound.
n-Butenes suitable for use in the present invention are commercially available from petroleum refinery operations. As already noted, such butenes should not contain more than l.5~ of isobutenes, because isobutene tends to ~orm products with a high degree of branching. Preferably the butenes consist substantially entirely oS l-butene, cis-2-butene and/or trans-2-butene. The presence of fully saturated hydrocarbons in the feed is not in general detrimental, but if the proportion rises above about 80 per cent by weight the process becomes uneconomic. The presence of olefins containing more than 4 carbon atoms per molecule should likewise be avoided because they reduce the selectivity of the reaction to produce octenes.
The nickel oxide on silica-alumina catalyst used in the present invention is known and has been described in, for example, United States Patent 2581228. It may be made by treating a calcined silica-alumina gel with a solution of a water-soluble nickel salt, and then with an agent to precipitate the nickel on the gel, e.g. as the hydroxide or carbonate. The silica-alumina gel with the nickel hydroxide or carbonate precipitated thereon is then filtered off and dried and calcined. The proportion of Nio is chosen to provide essentially what is equivalent to a monolayer of the Nio on the silica-alumina support. Smaller or larger amounts of Nio reduce W091/09826 PCT/GB~/02011 207~
catalyst actlvlty. The proportion of alumina i8 chosen to provide a high conver6ion rate combined with acceptable catalyst life. Too little alumina allows rapid catalyst deactivation, while too much qives poor conversion rates. It has been found that the tomperature of the calcination not only affects catalyst life but also can dramatically affect the isomer distribution in the mixture of octenes obtained in the new process. Preferably the catalyst is calcined at S00 to 700C so that a ~ixture containing a large proportion of octenes having an average of l.6 to 2.0 side chain methyl groups per molecule is obtained.
The reaction temperature must be at least 150 C in order to achieve the required conversion rate and average number of methyl groups per molecule. However, if the lS temperature is too high, the proportion of side chain methyl groups increase, and it is therefore desirable to use a reaction temperature below about 275 C. Preferably, the contact temperature is in the range of 175 to 225 C, and it is especially preferred to operate at a temperature in the range of 180 to 200 C. The pressure in the reaction zone must be sufficient to keep the butenes in the supercritical state at the operating temperature. In practice this requires a pressure in the range of about 50 to 200 bars, preferably about 70 bars.
As already indicated, the feed rate of the octene mixture should be such as to ensure a liquid hourly weight 2 ~ 7 317 8 -8-feed rate from o.4 to l.8, preferably 0.6 to 0.7 h-l. Above this feed rate the butene conversion falls to unacceptable levels and the number of side chain methyl groups per octene ~olecule fallc below l.6.
As already noted, when the butene feed contains ~ore than about 5 ppm of sulphur, derived from mercaptans, disulphides, hydrogen sulphide and the like, the poisoning effect of the sulphur can be counteracted by adding to tbe feed from S0 to 2,000 ppm of a nitrogen-containing compound.
Suitable nitrogen-containing compounds are aliphatic and saturated heterocyclic primary, secondary and tertiary amines containing l to 12 carbon atoms, e.g. mono-, di- or tri-ethyl- amine or a saturated heterocyclic amine such as pyrrollidine. It is believed that such nitrogen-containing lS compounds are effective because they prevent the sulphur-containing poisons in the butene feed from becoming bound to the nickel oxide catalyst and deactivating it. It is surprising that the nitrogen-containing compounds have this effect because at lower temperatures than those used in the present invention, such compounds are themselves regarded as catalyst poisons.
The process of the present invention does not require special apparatus and can be operated in any reactor configuration which is capable of promoting intimate contact between the butene feed and the cata~yst. The process can be operated batchwise, ~emi-batchwise, or continuously.
Continuous operation in a fixed bed reactor is preSerred.
WO 91/09826 PCI'/GB90/02011 9 .
Besides the desired octene mixture, the process of t~e present invention produces minor amounts of C5_7 and Cg_ 16 olefins. Of these the most important are the dodecenes, which in some cases are produced in a weight proportion as high as half that of the octenes. It is usually economically worthwhile to isolate and separate such by-product olefins.
The following Examples illustrate the invention:
Examples ~-24 The butene feed in these Examples was a commercial product which contained the following major ingredients and impurities:
EE~ IMPlJ~ IES
iso-butane : 4.3 wt% 1,3-butadiene : 350 ppmw n-butane : 14.5 acetylenics : ~10 ppmw 15 n-butene-l : 44.5 oxygenates (alcohols) : C 5 ppmw iso-butene : 1.2 ethers : < 5 ppmw trans-butene-2 : 22.0 sulfur : 2 ppmw cis-butene-2 : 13.5 chlorine : < 2 ppmw The butene mixture was passed over a 28 weight per cent Nio catalyst on a silica-alumina support containing 75 weight per cent silica and 25 weight per cent alumina, in the form of 3 mm tablets at a temperature in the range 185 to 195 C at a liguid hourly weight feed rate of about 0.6 to 25 ~1.6. The pressure in the reaction zone was maintained at 70 bars.
In the Tables:
a) W.W.H. is the liguid hourly weight feed rate, in the case of the hatch examples 44-61 this is defined as the wosl/o9826 PCT/CB90/02011 3~ o-inverse of the feed weight divided by the catalyst weight multiplied by the reaction time.
b) CATLIFE, WprOd/Wcat~ is the length of each experimental run measured as the ratio of weight product produced to weight of catalyst used.
c) Conversion is the percentage of butene feedstock reacted.
d) Select~ity is the ratio of a specific product to the amount of butene feedstock reacted.
ej Yield is selectivity x conversion.
"ISOMER DISTRIBUTION" is C8 isomer distribution and "av Branchiness" is the average number of methyl groups per molecule obtained by gas chromatographic analysis of the octene product after hydrogenation.
The following Table shows the results of 24 experiments:
WO 91/09826 ~ PCI/GB90/02011 In ~In~ ON 2a73~78 t rl ~ o~ ~ ~ ~ ~ g r~
I~
N
S r. ~ S
~ ~ N N 0 ~ 8 r, ~; ~ N N _ ~ ~ I;i ~ o ~"
o ~ ~ ~ N ~ o ~ ~ In O ~
N ~ O H - ~ 8 1~ ~ O ~ ~ H
H ~ 1~ ~ N 0~ ~ O ~ O ~ o ~1 N ~ H ~ N o N r~ g ~5 ~i 0 H ~O o 1~ 0 ~ ~1 N ~ O ~i N H
~ ~ ~ m o ~
g 0 O 1~ ~ ~ t~ N ' g - N ~ ~~ ~ ~ N ~ ~ ~ H O
H ~ , H~r ~ t~ H o o ~
n ,~ ~ ~ N rl ~ ~ g 8 ~3 , , WO 91/09826 - 12 - PCI`/GB90/02011 o . ~ O ~ . r~ ~ r, ~; o ~ ~ o ~ , . ,~ I` ~ ~ O g N r~ ~ ~1 ~ ' ~ N
N ~; 1` ~ 0 6 . .
~S ~ '~ ~ ~ O O ~ ~ O n o o ~
o o ~ ~ o ~ O o C ~n r~
O~ N
o I ~ j 1~1 1 . ,,~ ,, .
-13- 2 ~7 3 17 8 ~E~amples 25 to 4~
The butene feed in these Examples contained the following major ingredients and impurities:
E~ =~
iso-butane : 3.3 wt% 1,3-butadiene :4850 ppmw n-butane : 36.8 acetylenics :50 ppmw n-butene~l 33.0 oxygenates (alcohols) : 30-50 ppmw iso-butene : 1.4 Me2O : 50 ppmw trans-butene-2 : 15.9 Et2S : 8 ppmw as S
cis-butene-2 : 9.6 Me25 : 7 ppmw as S
Cl : < 2 ppmw The mixture of n-butenes was contacted with the same catalyst as that used in Examples 1 to 24 (in the for~ of 3 mm tablets) at the temperatures, pressures and contact times shown in the following table:
WO 9t/09826 PCl/GB90/02011 201 3~ 1~
1'1 N 1~ ~ ~; N ~'~N O ~ O t~
.n a~ ~ ' '' . ~ N O
~ N ~` ~ $ 1~ o " ~ ~ ~ ~4 I~ N ~ N ~ ~ O ~-- ~ r~ I N
N O O o ~ ~,~ g g O O
,~ nO Ci ~jj N N I
o~ g r~ o In ~ O
O ~I h ~ ~ o ~ ~ N ~ N ~ ~ ~ j~ O t~ O ~0 r~ ~1 N ~ B N
~ ~ ~ S ~ O
x ~ ~ ., Il, ., ~ ~ o 3 ~ g ~ O H g ~ ~ N ~ ' N
~ ~ ' N ~ ~ ~ ~ N H o o o~
N ~ t` rl O O ~ ~ ~1 0 0 0 1~ rl ~i 5 ~ ~ 'NN ", ~ r~ g 11~ ~ O ,~Iti ,~ O N ~ n ~
~ 8 WO 91/09826 PCl'/GB90/02011 O " ~ o ~ O ~O ; ~
5 ~ . i ~ ;2 " a ~ n H H ~ ~ æ
~: o o o n ~ o~ N ~ 8 N ~ 1 O 0 ~ O ~ O t~ ~ 1 o~ ~3 o ~ ô 1~ rl N ~ 8 ,~ E ~ æ
~ H ~ ~ O O
O N t~ N 1~ 0 ~ ~ O 0 ~ ~ ~i ~ o o ~ o 3 ~ ~ N ~ N ~O O
N ~ ~ ~ ~ ~ O r~
N ~ ~i ~ N ~-~ O O N ; ' ' 207 3~7 8 -16-Exam~lçs 44 to 50 In a furt~er 6eries of experiments pure n-butene-l was contacted with the same nickeloxide on silica-alumina catalyst at temperatures in the range 155 to 220 C and at contact times from 0.67 to 1.67 per hour with the results shown in the following table:
T~L~ 3 Ex .No~ W.W.H. Temp.C Percent. Conv. Average CH3/mol 44 0.67 180 81 1.77 1045 0.67 125 75 1.50 46 1.00 200 81 1.71 47 0.67 220 81 1.65 48 1.67 220 77 1.72 49 1.67 155 78 1.61 1550 1.00 155 78 1.65 These results show that too low a temperature gives too low a proportion of side chain methyl per molecule.
Examples 51-57 The same procedure as in Examples 44 to 50 was repeated usinq trans-2-butene as the starting material. The catalyst (which was the same as that used in Example 1) was crushed to 10-14 mesh particles and then calcined in an electric furnace at 500-C for 16 hours in flowing air. In a dry box, a 300 ml autoclave was loaded with the catalyst, a known weight of decane used as internal standard, and (where acid) an additive ~pentanethiol, pyrrolidine, diethyl disulfide). ~he autoclave was evacuated/N2-purqed three times, then charged decane used as internal ~tandard, and (where acid) an additive (pentanethiol, pyrrolidine, diethyl disulfide). The autoclave was evacuated/N2-pur~ed t~ree times, then charged with a known amount of high purity (>99%) butQne. Thi~ atep was followed ~y heating the autoclavQ to the s~t t~mperature for predetermined length of time with continuous 6tirring.
The butene/catalyst weight ratio and heating time corresponded to the space velocity indicated in Tabl- 4 below. At the end of th- run, the autoclave was cooled to ~5-C, vented to the air, and the liquid product was analysed by gas chromatography. The following results were obtained:
WO 91/09826 PCI/C;B90/02011 c~ --18--'l 3 ~r~ ~ o s V
. . . . . . .
. _ _ _ , , _ , D
~ ~ I
V ~C ~, O ~ /
O Cl.
v ~J ~ o~
_ ~ ~C ~
~ ll _ U
Ql IC 11~ 0 _~ C ~ _~ _ ~ O ~ ~ h~ _ u~ ~ r ~ ~ 0 dO ~ ~0 U~ U
C D
I
~ C
_ V~
~J ~ U
C ~ O~
a~ ~ c ~ u U C o r~ _ o ~ ~ o~
o , a~ CD ~ I` ~ I` .
w ~. ~ O.V a~
.. :) C
~ V V-~l E~ CL u~ C U V
E ~) t~ r u~ u~ u ~ _, ~o _ _ _ _ _ _ _ v a~ v E~ ~ ~ c ~ V
:r . v ~c o o o o o o o . . . .
3 _ _ _ _ _ , _ ~ ~ c a~ o ~0 c c ~ ~ s ~
:~ ' :) ") ~ D ~
_~ --o --o --O V C .
v E _ o ~o _o ~ ~_~
o u~ o o o o s s ~ c I V V
3 c c ~ ~ ~ c ~ ~ O
~C zO zO ~ ~ zo z ~ vo Vc Ea' S~
O E S C S QJ ~ ~- ~
., --~ ~ _ ~. ~q v 0 3 C--I c _ c ~ E C
G ~ J ~ tO ~ ~ ~ S ~ t s _ ~Q. ~ ~ O
v v v al v :~ I~ v ~ t~a, u, o t~
~ C C C C ~ U~ .
oa~ ~ a) o ~-- ---,-~ v ~J S Q
ZP~ ~ Z ~ ~ ~ ~ S ~
K O ~ D 1` _ _C~ O
~ Z U~ 7 U
C
E~mples 58-61 The same procedure as in Examples 44 to S0 was repeated using pure trans-2-butene as the starting mater~al and the same catalyst as that u~ed in Examples 51-58. The temperature and feed rate was varied as shown in the following Table which also shows the results obtained.
Ex. ~o W.W.H Tem~.C percent.Conv. AveraGe CH3~2~L
58 1.00 175 83 1.62 ~9 5.00 175 58 1.43 ~0 l.OO 95 72 1.58 :
61 5.00 95 44 1.39 These results show that too high a feed rate or too low an operating temperature fail to achieve the desired degree of j branching of the octene product.
Claims (10)
1. Process for the preparation of a mixture of isomeric octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule and containing not more than 8 per cent by weight of octenes having 3 side chain methyl groups per molecule which comprises contacting an n-butene at a temperature between about 150° and 275°C and in the supercritical state with a nickel oxide (Nio) catalyst containing 5 to 30 per cent by weight of Nio, on a silica-alumina support containing 10 to 45 per cent by weight of Al2O3 and having at least a surface area of 100 m2/g, at a liquid hourly weight feed rate of the said butene over the said catalyst of 0.4 to 1.8 h-1.
2. Process according to claim 1 in which said n-butene is present in a mixture containing at least 20 per cent by weight of butenes and not more than 80 per cent by weight of saturated hydrocarbons.
3. Process according to claim 2 in which said mixture contains not more than 1.5 weight per cent of isobutene.
4. Process according to any one of claims 1 to 3 in which the n-butene contains 1 to 40 ppm of sulphur.
5. Process according to any one of claims 1 to 3 in which the n-butene contains from 40 to 200 ppm of sulphur, and from 50 to 2,000 ppm of an organic nitrogen-containing compound is added to the n-butene.
6. Process according to any one of claims 1 to 4 wherein the said catalyst contains 20 to 30 per cent by weight of Nio of NiO and the surface area of the support is 100-450 m2/g.
7. Process according to any one of claims 1 to 6 in which the said liquid hourly weight feed rate is 0.6 to 0.7 h-1.
8. Process according to any one of claims 1 to 7 in which the said contact takes place at a temperature in the range 175 to 225° C.
9. Process according to any one of claims 1 to 8 in which the said nickel oxide catalyst on the silica-alumina support has been activated by calcination at a temperature of 500° to 700° C before use.
10. Process according to any one of claims 1 to 9 wherein the contact takes place at a pressure of 50 to 200 bars.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP90300159 | 1990-01-05 | ||
| EP90300159.2 | 1990-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2073178A1 true CA2073178A1 (en) | 1991-07-06 |
Family
ID=8205252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002073178A Abandoned CA2073178A1 (en) | 1990-01-05 | 1990-12-21 | Process for the preparation of octenes |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0509003A1 (en) |
| JP (1) | JPH05504948A (en) |
| CA (1) | CA2073178A1 (en) |
| WO (1) | WO1991009826A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI111463B (en) * | 2001-10-12 | 2003-07-31 | Fortum Oyj | A process for the preparation of an oxygenated gasoline component and a gasoline component |
| DE102004033410A1 (en) * | 2004-02-14 | 2005-09-01 | Oxeno Olefinchemie Gmbh | Preparation of higher olefins from lower olefins, useful to form alcohols and/or aldehydes, comprises hydroformylation of olefin to aldehyde, hydrogenation of the aldehyde to alcohol, removal of water and extraction |
| FI120627B (en) * | 2007-08-24 | 2009-12-31 | Neste Oil Oyj | Process for oligomerization of olefins |
| JP2014151253A (en) * | 2013-02-06 | 2014-08-25 | Jx Nippon Oil & Energy Corp | Method for low polymerization of olefin, and catalyst used for the method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2642467A (en) * | 1950-05-11 | 1953-06-16 | Phillips Petroleum Co | Production of high octane fuel components |
| US3658935A (en) * | 1970-06-08 | 1972-04-25 | Exxon Research Engineering Co | Dimerization and codimerization process |
-
1990
- 1990-12-21 EP EP91901320A patent/EP0509003A1/en not_active Withdrawn
- 1990-12-21 WO PCT/GB1990/002011 patent/WO1991009826A1/en not_active Application Discontinuation
- 1990-12-21 JP JP3501709A patent/JPH05504948A/en active Pending
- 1990-12-21 CA CA002073178A patent/CA2073178A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0509003A1 (en) | 1992-10-21 |
| JPH05504948A (en) | 1993-07-29 |
| WO1991009826A1 (en) | 1991-07-11 |
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