NL8500459A - METHOD FOR OLIGOMERIZING OLEFINS. - Google Patents

Description

1 N.0. 32994 *

Process for oligomerizing olefins »

The present invention is in the field of oligomerizing olefins. More particularly, the present invention relates to oligomerization of liquid phase olefins with a nickel-containing, silicon-containing, crystalline molecular sieve-5 catalyst.

Gas phase oligomerization and polymerization of olefins over various zeolites is known in the art. For example, U.S. Pat. No. 3,960,978 discloses a process for the preparation of a gasoline fraction containing predominantly olefinic compounds, the process of contacting an alkene of 2 to 5 carbon atoms with a crystalline aluminosilicate zeolite of the ZSM- Type at a temperature of from about 260 ° C to about 480 ° C.

U.S. Patent 4,021,502 describes the conversion of 15 gaseous olefins of 2 to 5 carbon atoms to a gasoline blending stock by passage over ZSM-12 at temperatures from about 205 ° C to 650 ° C.

U.S. Patent 4,211,640 describes a process for treating a highly olefinic gasoline containing at least about 20 to 50 wt.% Olefins by contacting this olefinic gasoline with crystalline aluminosilicate zeolites such as those of the ZSM-5.

i type, to selectively convert olefins other than ethylene and to produce both gasoline and fuel oil.

US Patent 4,254,295 describes a process for the oligomerization of olefins by contacting these olefins in the liquid phase with a ZSM-12 catalyst at temperatures from 26.7 ° C to 204 ° C.

US Patent 4,227,992 describes a process for separating ethylene mixed with light olefins by contacting this olefinic mixture with a ZSM-5 catalyst and thus producing products in both the gasoline and fuel range.

The processes described in these patents differ from those of the present invention in that they employ a different catalyst, higher temperatures or gaseous reaction.

Also, an important feature of various catalysts used in these prior art processes is that BAD OBI-Phytolyser for oligomerization must have reduced activity.

«R 0 Π 6 RQ

2 am. Such a reduced activity catalyst can be obtained by steaming or by use in a preliminary conversion process.

This deactivation step is not required in the process of the present invention.

In accordance with the present invention, there has been found a process for oligomerizing olefins comprising: (a) contacting an olefin having 2 to 20 carbon atoms or a mixture thereof in the liquid phase with a nickel-containing, crystalline crystalline molecular sieve in the hydrogen form selected from the group consisting of HZSM-5, HZSM-11, crystalline mixtures of HZSM-5 and HZSM-11, silicalite, an organosilicate described in SE 29948 and CZM or mixtures thereof, at a temperature of about 7 ° C to about 235 ° C; (b) recovering a effluent containing oligomerized olefin 15.

It has been found that the present process provides selective conversion of the olefin feed to oligomeric products. The present process accomplishes the conversion of the olefin feed to dimer, trimer, tetrameric, etc. products with high selectivity. Thus, the product of the present reaction primarily contains ethylenically unsaturated oligomer and little or no light cracked products, alkanes, etc.

The high selectivity is due in part to the surprisingly high oligomerization activity of the catalyst of the present process, which allows for high conversion at low temperatures, with cracking reactions being minimized.

The oligomers, which are the products of the process of the present invention, are medium to heavy olefins, which are highly useful for both fuels and chemicals. These include olefinic gasoline, such as from dimerization of propylene and mid-boiling cylinder boilers of extremely high quality, such as jet fuel. Higher molecular weight compounds can be used without further reaction as components of functional fluids such as lubricants, as agents for improving the viscosity index in lubricants, as hydraulic fluids, as transmission fluids and as insulating oils, eg in transformers to replace PCB containing oils. These olefins can also undergo chemical reactions to form surfactants which in turn can be used as additives to improve the operating properties of the compositions to which they have been added (eg lubricating oils) or used as primary surfactants in key activities such as improved oil recovery or as detergents. The most commonly used surfactants, which are administered from these heavy olefins, include alkyl sulfonates and alkyl aryl sulfonates.

An essential feature of the present process is contacting the olefin feed and the nickel-containing, silicon-containing, crystalline molecular sieves in the liquid phase. It will be understood that the pressures and temperatures used must be sufficient to maintain the system in the liquid phase. As will be known to those skilled in the art, the pressure will be a function of the carbon number of the olefin feed and the temperature.

The oligomerization process described herein can be performed as a discontinuous, semi-continuous or continuous type operation using a fixed or moving bed catalyst system.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a graph showing conversion of propylene 20 to higher molecular weight products as a function of time at 54 ° C, 11,030 kPa and 0.5 LHSV (LHSV »parts by volume of gas per part by volume of catalyst per hour) for two different catalysts. _

Fig. 2 is a graph showing the selectivity of the carbon number for the oligomerization of propylene at 54 ° C, 11,030 kPa and 0 * 5 LHSV for two different catalysts.

Fig. 3 is a graph showing an expansion of the temperature for a 90% conversion of propylene to C5 + over a Ni-Zn-HZSM-5 catalyst over time under the proposed conditions.

Fig. 4 is a graph showing temperature expansion for a 70% conversion of a Cg-C9 gasoline feed to a higher boiling product over time over Ni-Zn-HZSM-5 and Zn-HZSM-5 catalysts under the proposed circumstances.

FIG. 5 is a gas chromatogram of the product of Example XIX.

Fig. 6 is a graph showing an expansion of the temperature for a conversion of 70% C5-C9 gasoline feed to a higher boiling product over time over Ni.-Zn-HZSM-5 under the above conditions.

BAD ORIGINAL

8500459 k 4 DESCRIPTION OF SPECIFIC EMBODIMENTS The feeds used in the process of the invention contain olefin which are liquids under the conditions in the oligomerization reaction zone. Under standard operating methods, it is normal to know the chemical composition of feedstocks fed into a reaction zone as well as adjusting and controlling the temperature and pressure in the reaction zone. Once the chemical composition of a feed is known, the temperature and the partial hydrocarbon pressures, which may be all or part of the feed as. 10 fluids will be maintained using standard tables or routine calculations. Conversely, once the desired temperature and pressure to be applied have been set in the reaction zone, it becomes a matter of routine to determine which feeds and feed components will or will not be liquids in the reactor. 15 These calculations involve the use of critical temperatures and pressures. Critical temperatures and pressures for pure organic compounds can be found in standard reference books such as CRC Handbook of Chemistry and Physics, International Critical Tables, Handbook of Tables for Applied Engineering Science, and Kudchaker, Alani 20 and Zwolinski, Chemical Reviews 68, 659 (1968). The critical temperature for a pure compound is that temperature above which the compound cannot be liquefied regardless of the pressure. The critical pressure is the vapor pressure of the pure compound at its critical temperature. These points for various pure olefins are set forth below: T * C _ (* F) P ^ -atm (bar) ethylene 9.21 (48.6) 49.66 (50.3) propylene 91.8 ( 197.2) 45.6 (46.2) 1-butene 146.4 (295.5) 39.7 (40.2) 30 1-pentene 191.59 (376.9) 40 (40.5) iso -2-pentene 203 (397) 36 (36.5) 1-hexene 230.83 (447.49) 30.8 (31.2) 1-heptene 264.08 (507.34) 27.8 (28. 2) 1-octene 293.4 (560.1) 25.6 (25.9) 35 1-decene 342. (648) 22.4 (22.7) 0 »

It turns out that at temperatures above about 205 ° C (401 ° F), pure C5 and minor molecular olefins must be gaseous, while pure C * and larger molecular olefins can still be liquefied by using BAD ORIGINAu 40 pressure. Similarly, above about O C Λ A /. C t% -s'. *.

5 275 ° C (527 ° F) pure Cg and higher molecular weight olefins are kept in the liquid state, while pure C7 and lower molecular weight olefins must be gaseous.

Usual feeds are mixtures of compounds. But even in that case, once the chemical composition of the feed is known, the critical temperature and pressure of the mixture can be determined from the proportions of the chemicals and the critical points of the pure compounds. See, for example, Kay and Edmister's methods in Perry's Chemical Engineers Handbook, 4th ed., 10 pages 3-214, 3-215 (McGraw Hill, 1963).

Obviously, the only limitation of the olefins present in the feed to be converted in the oligomerization reaction zone is that these olefins are liquids under the conditions in the reaction zone (the conditions include a temperature of less than about 235 ° C). The chemical composition of the olefins can be varied to obtain any desired reaction mixture or product mixture, as long as at least some of the olefin components of the feed are liquid.

The olefin chains can be branched. Even though the nickel-containing, siliceous, crystalline molecular sieve catalysts used in the present invention are molecular sieves with an intermediate pore size, olefins having quaternary carbon atoms (two branches on the same carbon) can be used. But.

When quaternary carbon atoms are present, it is preferable that the branches are methyl.

The preferred olefins have straight chain or n-olefins and the preferred n-olefins are 1-olefins. The olefins have 2 to 20 carbon atoms and more preferably have about 2 to about 6 carbon atoms.

One of the surprising discoveries of the present invention is that under certain reaction conditions, longer chain olefins can be polymerized instead of being cracked into short chain compounds. Also, the oligomers made from long n-1 olefins are highly desirable for use as lubricants. The 35 oligomers have surprisingly little branching, so they have very high viscosity indices, yet they have enough branching to have very low pour points.

The feed olefins can be prepared from any source according to standard methods. Sources of such olefins may include FCC.

B / WORfGU & fe, coker effluent, synthesis gas (using 8500459 »6 CO reduction catalysts), low pressure, non-hydrogenating zeolite dewaxing, alkanols (using high molecular weight silica * zeolites) and crystalline silicon dioxide dewaxing polymorphs. Highly suitable n-1 olefin feeds, especially for preparing lubricating oil base stocks, can be obtained by thermal cracking of hydrocarbonaceous compositions containing normal paraffins or by the polymerization of ethylene by Ziegler.

Often suitable feeds are prepared from lower molecular weight olefins self-polymerized. Such feeds include polymeric gasoline of the mass H3PO4 polymerization and propylene dimer and other olefinic polymers in the C4-C20 range prepared by art-known procedures.

The nickel-containing, silid-containing crystalline molecular sieves used in the present invention are of intermediate pore size. "Intermediate pore size," as used herein, is understood to mean an effective pore opening in the range of about 0.5 to 0.65. nm, when the molecular sieve is in the H form. Molecular sieves with pore openings in this range lead to 20 unique molecular sieving properties. Unlike small pore zeolites such as erionite and chabazite, they will allow some branching hydrocarbons into the voids of the molecular sieve. Different from zeolites with large pores, such as the faujasites. and murmurs, they can differentiate between n-alkanes and slightly branched alkanes, on the one hand, and larger branched alkanes with, for example, quaternary carbon atoms.

The effective pore size of the molecular sieves can be measured using standard adsorption techniques and hydrocarbonaceous compounds of known minimum kinetic diameters. See, 30 Breek, Zeolite Molecular Sieves, 1974 (especially chapter 8) and Anderson CjS., J. Catalysis 58, 114 (1979).

H-form intermediate pore size molecular sieves will usually allow molecules with kinetic diameters from 0.5 to 0.65 nm with little hindrance. Examples of such compounds (and their kinetic diameters in nm) are: n-hexane (0.43), 3-methylpentane (0.55), benzene (0.585) and toluene (0.58). Compounds with kinetic diameters of about 0.6 to 0.65 nm can be admitted into the pores depending on the particular screen, but penetrate BAD and in some cases are adequately excluded. Up to 40 compounds with kinetic diameters in the range 0.6 to 0.65> 7 am include: cyclohexane (0.60), 2,3-dimethylbutane (0.61), mr-xylene (0.61) and 1,2,3,4-tetramethylbenzene (0.64). Generally, compounds with kinetic diameters greater than about 0.65 nm do not penetrate the pore openings and thus are not absorbed into the interior of the molecular sieve screen. Examples of such larger compounds include: o-xylene (0.68), hexamethylbenzene (0.71), 1,3,5-trimethylbenzene (0.75) and tributylamine (0.81).

The preferred effective pore size range is from about 0.53 to 0.62 nm.

Standard techniques are used when performing adsorption measurements to determine the pore size. It is expedient to consider a particular molecule to be excluded if it does not reach at least 95% of its equilibrium adsorption value on the zeolite in less than about 10 minutes (p / po * 0.5; 25 ° C).

Nickel-containing HZSM-5 is described in U.S. Pat. Nos. 3,702,886 and 3,770,614.

HZSM-11 is described in U.S. Patent 3,709,979. "Crystalline mixtures" of ZSM-5 and ZSM-11 also exist, which are thought to result from errors occurring within the crystal or crystallite region during the synthesis of the zeolites.

The "crystalline mixtures" are themselves zeolites but collectively have properties, in a uniform or non-uniform manner, which the literature mentions as different zeolites. Examples of crystalline mixtures of ZSM-5 and ZSM-11 have been described in the American. Pat. No. 4,229,424 The crystalline mixtures are themselves intermediate pore size zeolites and should not be confused with physical zeolite mixtures in which different crystals or crystallites of different zeolites are physically present in the same catalyst composition or hydrothermal reaction mixture.

Sillcalite is described in U.S. Patent 4,061,724; the "RE 29,948 organosilicates" are described in RE 29,948; chromium oxide silicates, CZM, are described in United States Patent Application 450,419 filed December 16, 1982, in Canadian Application No. 358,973 filed August 22, 1980, and in British Patent Application No. 35 2,056,961.

The so-called "RE 29 * 948 organosilicates" are defined in both this US re-issue patent and in the original US patent 3,941,871 as follows: "A crystal metal organosilicate of a composition, in its water-free" state, expressed in molar ratios of oxides as BAC0P5I0HW 5 9 8 follows: 0.9 + 0.2 [xR20 + (1x) M2 / 0]: <0.005 Al2C> 3:> SiO2 'n 5 in which M sodium or sodium in combination with tin, is calcium, nickel or zinc, R is a trialkylammonium and x is a number greater than zero but no greater than 1, which organosilicate has the X-ray diffraction lines as listed in Table 1 of the description "*"

Table 1 contains approximately 16 lines for different interplanar distances. The four. main ones appear as a very strong line for a distance of 0.385 + 0.007 nm and strong lines at 0.371 + 0.005 nm, 1.00 + 0.02 nm and 1.11 + 0.02 nm »

The crystalline silicon dioxide polymorphs, silicalite and RE 29,948 organosilicates and the chromium oxide silicate CZM are substantially free of aluminum oxide.

. " "Substantially free from alumina," as used herein, means the product silica polymer polymorph (or substantially alumina-free, silica-containing, crystalline molecular sieve) having a silica: alumina molar ratio of greater than 200: 1, preferably greater than 500: 1. The expression "substantially free from alumina" is used because it is difficult to make all-aluminum? prepare your reaction mixtures to synthesize these products. Especially when commercial silica sources are used, aluminum is almost always present in varying degrees. The hydrothermal reaction mixtures from which the substantially alumina-free crystalline silica-containing molecular sieves are prepared may also be referred to as substantially free of aluminum. By this use is meant that no aluminum is added intentionally to the reaction mixture, for example as an alumina or aluminate reagent, and to the extent that aluminum is present it only occurs as impurity in the reactants.

The most preferred molecular sieve is the zeolite Ni-HZSM-5 and the Ni-containing hydrogen form of silicalite. Of course, these and the other molecular sieves can be used in physical mixtures.

When synthesized in the alkali metal form, the zeolites can be efficiently converted to the hydrogen form according to known ion exchange reactions, for example, by intermediate formation of the ammonium form as a result of ammonium ion exchange and calcination of eADd® RJ & JNAUv form to form the hydrogen form, as described 85 0 0 4 59 9, U.S. Patent 4,211,640, or by treatment with an acid, such as hydrochloric acid, as described in U.S. Patent 3,702,886.

Nickel is incorporated into these siliceous crystalline molecular sieves by methods known in the art, such as impregnation and cation exchange. For example, conventional ion exchange techniques will be to contact the hydrogen form of the particular screen with an aqueous solution of a nickel salt. Although a number of different salts can be used, chlorides, nitrates and sulfates are particularly preferred. The amount of nickel in the zeolites ranges from 0.3 to 10% by weight, and preferably from 1 to 5% by weight.

Representative ion exchange techniques have been described in a number of different patents such as U.S. Pat. Nos. 3,140,249, 3,140,251, 3,960,978, and 3,140,253.

After contact with the brine, the zeolites are preferably washed with water and dried at a temperature ranging from 66 ° C to about 260 ° C and then heated in air at temperatures ranging from about 260 ° C to 540 ° C for time-20 periods ranging from 1 to 48 hours or longer.

The nickel-containing, siliceous, crystalline molecular sieve catalysts can be made considerably more stable for oligomerization by about 0.2 to 3% by weight and preferably 0.5 to 2% by weight of the Group IIB, zinc or cadmium metals, and preferably 25 to include zinc. A primary characteristic of these substituents is that they are weak bases and are not easily reduced. These metals can be incorporated into the catalysts using conventional film-precipitation, ion-exchange, etc. techniques. Strongly basic metals, such as the alkali metals, are unsatisfactory,

30 since they poison virtually all polymerization sites of the zeolite. For this reason, the alkali metal content of the zeolite is less than 1%, preferably less than 0.1% and most preferably less than 0.01%. The feed should be low in water content, ie less than 100 ppm, more preferably less than 10 ppm, low sulfur content, ie less than 100 ppm, and preferably less than 10 ppm, low diolefin content, less than 0 , 5%, preferably less than 0.05%, and most preferably less than 0.01%, and especially low nitrogen content, ie less than 5 ppm, preferably less than .1 ppm, and most preferably have less than 0.2 ppm-BADOBiGINAL

e c η n /. c n 10

The polymerization processes of the present invention are surprisingly more effective with small crystallite sieve particles than with larger crystalline particles. Preferably, the molecular sieve crystals or crystallites are less than about 10 microns, more preferably. Less than about 1 micron, most preferably less than about 0.1 micron in the largest dimension. Methods for the preparation of molecular sieve crystals in various physical size ranges are known in the art.

The molecular sieves can be formulated with inorganic matrix materials or they can be used with an organic binder. It is preferable to use an inorganic matrix since the molecular sieves, due to their large internal pore volumes, lead to breakage and are subject to physical failure or attrition during the normal loading and unloading of the reaction zones 15 as well as during the oligomerization processes. When an inorganic matrix is used, it is highly preferred that the matrix be substantially free of hydrocarbon conversion activity. It will be appreciated that when an inorganic matrix having a hydrogen transfer activity is used, a significant portion of the oligomers generated by the molecular sieve can be converted to alkanes and aromatics and that a significant amount of the benefits of the present invention is lost.

The reaction conditions under which the oligomerization reactions take place include partial hydrocarbon pressures sufficient to maintain the desired olefin reactants in the liquid state in the reaction zone. Obviously, the larger the olefin molecules, the lower the pressure required to maintain the liquid state at a given temperature. As described above, the operating pressure is closely related to the chemical composition of the feed, but can be easily determined. Therefore, the required hydrocarbon partial pressure can range from 3100 kPa at 232 ° C for a pure n-1-hexene feed to about atmospheric pressure with an n-1-C 15 “C 20 olefin mixture. In the process of the present invention, both reagent and product are liquids under the reaction zone conditions, thus leading to a relatively long residence time for each molecule in the catalyst.

The reaction zone is usually operated below about 235 ° C. Above that temperature not only a significant cracking of B (AD & ISyQlfe & l * and loss of oligomer product takes place, but also significant fi n η n /. R λ 11 hydrogen transfer reactions, causing loss of olefin oligomers to alkanes and aromatics. An oligomer slat temperature In the range of from about 32 ° C to 180 ° C, LHSV may range from 0.05 to 20, preferably from 0.1 to about 4.

Once the effluent from the olgomerization reactor is obtained, a number of further processing steps can be performed.

When it is desired to use the long chain compounds formed in a bulk distillate fuel such as jet, diesel or lubricating oils as a base stock, the olefin oligomers are preferably hydrogenated.

All or part of the effluent may be contacted with the molecular sieve catalyst in other reaction zones to further react unreacted olefins and olefin oligomers with themselves and each other to form even longer chain products. Obviously, the longer the carbon chain, the more sensitive the compound to cracking.

Therefore, when successive oligomer slation zones are used, the conditions in each zone should not be so severe that the oligomers are cracked. The series oligomerization zones can also facilitate process control of the exothermic oligomerization reactions.

A particularly desirable mode of operation is to separate unconverted olefins present in the effluent from the olefin oligomers contained in the effluent and then recycle the unconverted olefins to the feed.

The following examples further illustrate the present invention. ·

Example I

HZSM-5 zeolite with a molar ratio of 80 S102 / A1203 was mixed with peptized Catapal alumina at a 50/50 sieve / aluminum oxide weight ratio, extruded through a 1.6 mm nozzle, dried at 149 ° C under N2 overnight and then in air calcined at 454 ° C for 8 hours. The catalyst was exchanged five times with a 1% aqueous ammonium acetate solution and then washed with water to give a final Na content of 100 ppm.

Example II

B / ORS ORIGIhlWL ^ atatizer of Example I was impregnated according to the polar filling method with 1% Zn below. using an aqueous zinc nitrate solution, then dried and calcined as in Example I.

Example III

The catalyst of Example I was exchanged with a 1-pro—

cents solution of nickel acetate in water at 82 ° C for 5 hours, washed with water, then dried and calcined as in Example 1 * The Ni content of the calcined catalyst was 3% by weight. Example IV

The catalyst of Example III was impregnated with 1% Zn, dried and calcined as in Example I *

Example V

The catalyst of Example II (Zn-HZSM-5) was tested for conversion of propylene to higher molecular weight products at 54 ° C, 11,030 kPa and 0.5 LHSV. After 40 hours of operation, the conversion to C5 + was less than 20 wt% (Fig. 1) with a selectivity of 32 wt% to dimer (Fig. 2).

The propylene dimer distribution is given in Table A.

20 Table A

C $ olefin composition of propylene olomeromerate C /; olefin selectivity% / 4-m-2-C5 «14.6 25 3-, 4-111-I-C5 * 9.4 2-m-2-C5- 32.2 2-mr-1-C5“ 4, 3 3-m-2-C5 "10.4 n-C6-0.8 30 2.3-dm-C4" 28.3

Example VI

The catalyst of Example IV (Ni-Zn-HZSM-5) was tested for propylene conversion under the same conditions as in Example V. After 40 hours of operation, the conversion to C5 + was greater than 98% by weight (Figure 1) with selectivity to dimer at 71% by weight (Fig. 2). This shows the surprising advantage of Ni addition to HZSM-5 expressed in both activity and selectivity to dimer. The propylene distribution is BAo8Wdteiu? S data · 13

Table B

Cg olefin composition of propylene oligomerization 5 Cfi olefin selectivity%.

4-10-2-05 = · 50.7 3-, 4 * m. "L ** C5a 6.1 2-m-2-C5 = 8.7 2-ml-C5" 1.2 10 3- m-2-C5 = 0.2 n-Cg = 26.8 2.3-dm-C431 6.3

Example VII

For comparison, a 5% NI on amorphous SIO2 / AI2O3 was prepared by porous filling impregnation of a 40/60 SIO2-AI2O3 bullet with an aqueous nickel acetate solution, drying overnight at 149 ° C followed by calcination in air at 454 ° C for 8 hours . When tested for propylene conversion under the conditions of Example V, the conversion to C5 + in 40 hours of operation was 54 wt% with 40 wt% selectivity to dimer.

Example VIII

The catalyst of Example III (Ni-HZSM-5) was tested for propylene conversion at 11,030 kPa and 1.0 LHSV. After 200 hours of operation, the conversion to C5 + was 73% by weight at 49 ° C.

Example IX

The catalyst of Example II (Zn-HZSM-5) was tested for propylene conversion at 0 kPa, 288 ° C and 2 LHSV under olefin gas phase conditions. After 90 hours of operation, the conversion was up to C5 + 80% by weight.

30 Example X

The catalyst of Example III (N1-HZSM-5) was tested for propylene conversion at the same conditions as in Example IX. After 70 hours of operation, the conversion was up to C5 + 30% by weight. This shows that the addition of Ni to HZSM-5 is beneficial only when the oligomerization is carried out under substantially liquid phase conditions.

9

Example XI

The catalyst of Example IV (Ni-Zn-H!? SM-5) was tested for propylene conversion at 0.5 LHSV and 11,030 kPa. Expansion of the catalyst temperature for a 90 percent conversion to C5 + against the BAVoftelfato * 1 is shown in Figure 3. After 430 hours of operation, the reaction

RiWIIUüa 14 tor pressure reduced to 5515 kPa. The catalyst was run for 800 hours before a temperature of 82 ° C was required for 90 percent conversion to C5 +. Product inspections are listed in Table C.

5 Table C

C5 + product inspections of the oligomerization of propylene at 6895 kPa and 0.5 LHSV

temperature ° C 49 10 conversion to C5 +, wt% 85 density, API 74.0 research octane number, pure 94.0

simulated TBP distillation LV%, eC

10/20 57.8 / 59.4 15 30/50 60.6 / 67.8. 70/90 71.7 / 139.4 alkanes, LVZ 0 olefins, LV% 100 naphthenes, LV% 0 '20 aromatics, LV% 0

Examples XII-XVI

The catalyst of Example I was impregnated with transition metals, which are known in the art as active to promote the oligomerization of light olefins. These include Co, Cu, Pd, V, and Cr. The results in Table D show that these catalysts are much less active than Ni-HZSM-5.

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o K η n /, r o 15

Table D

Conversion of propylene to C5 + products over a transition metal - HZSM-5 catalyst 5 at 54-66 ° C, 0.5 LHSV and 11,030 kPa. '* v

Example metal% loading wt% conversion ____________ _ ______________ at 40 hours XII Co 2.4 12 10 XIII Cu 0.5 <5 XIV Pd 2.5 <10 XV V 1.6 <10 XVI Cr 5 <5 VI Ni 3 98 15

Example XVII

The catalyst of Example II (Zn-HZSM-5) was tested to convert an olefinic C5-C9 gasoline feed (Table E) to a higher boiling product. The catalyst temperature for a conversion of 70% to 177 ° C + as a function of the operating time at 5515 kPa and 0.5 LHSV is shown in Figure 4. The rate of catalyst fouling at these conditions was about -0.09eC / hour.

Table E

25 Inspections of C5-C9 olefinic gasoline density, eAPI 69.8 research octane number, pure 95.5

D-86 distillation, LV%, * C

30. 10/20 66.6 / 68.9 30/50 70 / 72.2 7Pi90 87.8 / 175.6 alkanes, LV% 0 olefins, LV% 99 35 naphthenes, LV% 0 aromatics, LV% 1

Example XVIII

The catalyst of Example IV (Ni-Zn-HZSM-5) was added; u BAD ÖhldWS ^? the supply as in example XVII and with the same di L 'π η δ rq 16

After 100 hours of operation, the catalyst temperature was 127 ° C (Figure 7), about 77 ° C lower than necessary with Zn-HZSM-5. At more than 250 hours, the fouling rate was only £0.02 ° C / hour, a fourth or less than that for Zn-HZSM-5, demonstrating the benefit of the Ni addition to the catalyst with Cg + ^ olefinic feeds. A gas chromatogram of the product is shown in Figure 5.

Example XIX

The catalyst of Example III (Ni-HZSM-5) was run with the same feed as in Example XVII and at the same pressure, but with a higher feed rate (1 and 2 LHSV). Even at 2 LHSV, the contamination rate was only 0.056 ° C / h (Fig. 6), less than that for Zn-HZSM-5 at only 0.5 LHSV.

Example XX.

A Zn silicalite catalyst was prepared in the following manner »15 H silicalite with a molar ratio of 240 SIO2 / AI2O3 was mixed with peptized and neutralized Catapal alumina at a 67/33 sieve / alumina weight ratio, extruded through a 1.6 mm nozzle , dried overnight at 149 ° C under N2 and then calcined in air at 454 ° C for 8 hours. The catalyst 20 was impregnated by the pore filling method to 1 wt% Zn using a solution of Zn (NO 3) 2 in water, then dried and calcined as before.

Example XXI

The catalyst of Example 1 was impregnated up to 3 wt% Ni by the pore filling method using a solution of Ν1 (Νθ3.) 2 · 6Η2θ in water. The catalyst was dried overnight under N2 and then in air at 454 ° C for 8 hours

calcined

Example XXII

The Zn silicalite catalyst of Example 1 was tested for the conversion of propylene to higher molecular weight products at 66 ° C, 6.9 kPa, and 0.5 LHSV. After 24 hours of operation, the conversion was up to C5 + 3.2% with a selectivity to dimer of 38%.

Example XXIII

The Ni-Zn silicalite catalyst of Example II was tested for the conversion of propylene under the same conditions as in proceeding.

III. After 40 hours of operation, the conversion to C5 + 72.7% was a selectivity to dimer of 77%.

8 SWs 9

Claims (15)

1. A process for oligomerizing olefins, characterized in that (a) a C2 to C20 olefin or mixture thereof is contacted in the liquid phase with a nickel-containing, crystalline, crystalline molecular sieve in the hydrogen form selected from the group consisting of HZSM-5, HZSM-11, crystalline mixtures of HZSM-5 and HZSM-11, silicalite, an organosilicate described in RE 29948 and CZM or mixtures thereof, at a temperature from about 7.2 ° C to about Spring 235eC and (b) recover a effluent containing oligomerized olefin. 2. Process according to claim 1, characterized in that a nickel-containing, silicon-containing crystalline molecular sieve is used, which also contains zinc cation. Process according to claim 1 or 2, characterized in that the reaction is carried out at an LHSV of about 0.2 to 5. Process according to claims 1 to 3, characterized in that a pressure of from about 345 to about 11,030 kPa is applied. 5. Process according to claims 1 to 4, characterized in that HZSM-5 is used as the nickel-containing, silicon-containing, crystalline molecular sieve. Process according to claims 1 to 4, characterized in that HZSM-11 is used as the nickel-containing, silicon-containing, crystalline molecular sieve. Process according to claims 1 to 4, characterized in that a crystalline or physical mixture of HZSM-5 and HZSM-11 is used as the nickel-containing, silicon-containing, crystalline molecular sieve. 8. Process according to claims 1 to 4, characterized in that the nickel-containing, silicon-containing, crystalline molecular sieve is used with silicalite · Process according to Claims 1 to 4, characterized in that an organosilicate as described in RE 29.948 is used as the nickel-containing, silicon-containing, crystalline molecular sieve. 10. Process according to claims 1 to 4, characterized in that CZM is used as the nickel-containing, silicon-containing, crystalline molecular sieve. Process according to Claims 1 to 10, characterized in that BAD uses olefin alkenes. 12. Process according to claim 11, characterized in that 1-olefins are used as 40 n-olefins. fi * 5 n n L K n Process according to claims 1 to 10, characterized in that olefins containing branched chain olefins are used and wherein the branches of the branched chain olefins are methyl branches. 14. Process according to claims 1 to 13, characterized in that the olefin oligomers are hydrogenated. Process according to claims 1 to 14, characterized in that unreacted olefins present in the effluent are separated from olefin oligomers, which are present in the effluent, and the unreacted olefins are recycled to the feed for the contact stage · I H4I II BAD ORIGINAL fi R Λ Π /, R n