CA1067880A - Process for the fluoriding of a catalyst - Google Patents
Process for the fluoriding of a catalystInfo
- Publication number
- CA1067880A CA1067880A CA246,844A CA246844A CA1067880A CA 1067880 A CA1067880 A CA 1067880A CA 246844 A CA246844 A CA 246844A CA 1067880 A CA1067880 A CA 1067880A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- fluorine
- slip
- weight
- parts
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
ABSTRACT
A uniform distribution of fluorine over a fixed bed of catalyst particles is obtained by in-situ fluoriding with the use of a constant or variable fluorine slip through the catalyst bed combined or not combined with a positive temperature gradient over the bed, provided that certain given requirements with respect to the applied fluorine slip and temperature gradient are fulfilled.
A uniform distribution of fluorine over a fixed bed of catalyst particles is obtained by in-situ fluoriding with the use of a constant or variable fluorine slip through the catalyst bed combined or not combined with a positive temperature gradient over the bed, provided that certain given requirements with respect to the applied fluorine slip and temperature gradient are fulfilled.
Description
38~
The invention relates to a process for the fluoriding of a catalyst.
For a number of catalytic processes, the suitability of the catalyst can be improved by incorpo~ting fluorine therein. Incorporation of fluorine in catalysts can basically be effected in two manners. Fluorine can be incorporated in the catalysts during their preparation, for example by impregnation of the carrier with a suitable fluorine compound. It is also possible to ineorporate fluorine in the finished catalyst prior to or during the initial phase of the process for which the catalyst is utilized, by addition of a sl~ table fluorine compound to a stream of gas and/or liquid which is passed over the catalyst. If desired, the latter fluoridin~ technique, which is generally referred to as in-s1tu fluoriding, may be combined with the impregnation technique mentioned before.
Durin~ in-situ fluoriding, fluorine produced by dec~mposition of the utilized fluorine compound under the prevailing reaction conditions i~ absorbed by the catalyst. In practice, the in-situ fluoriding process is continued until the catalyst has absorbed the calculated quantity of` fluorine. In this case the conditions are so chosen that rirtually sll the fluorine supplied to the catalyst is in fact absorbed thereby.
During an investigation carried out by the Applicant into the in-situ f`luoriding of a fixed bed of catalyst particles, it has been established that the above-described technique as a rule leads to a non-uniform distribution of fluorine over the catalyst bed, with an excess of fluorine in the first part of the bed and a deficiency thereof in the final part of the bed. In processes where optimum eatalyst perforrnance is dependent on a given minimum quantity of fluorine on the catalyst, a non-uniform distribution of fluorine over the eatalyst bed eauses no harm, provided that the requisite minimum quantity of fluorine is present throu~hout the catalyst bed. In most eases, however, optimum eatalyst performance is dependent on a given fixed fluorine eontent and the perrormance of the catalyst is worse if its fluorine '7~
!
content is above or below that fixed level.
It has been found that during the in-situ fluoriding of a fixed bed of catalyst particles a uniform dis~ribution of fluorine over the bed can be obtained if use is ~ade of a constant fluorine slip throu~h the bed combined or not combined with a positive temperature gradient over the bed, the conditions to be met being as follows:
(a) '~he average fluorine slip (SA) should be at least 10 %w. A fluorine slip is de~ined as the percentage by weight of the supplied quantity of fluorine which is not absorbed by the catalyst bed. Because of the fact that during the initial and the final stage of the in-situ f fluoriding, as well as, to a lesser degree, during the course of the in-situ fluoriding fluctuations in the fluorine slip cannot be avoided, the concept of "in-situ fluoriding with the use of a con3tant fluorine slip" should not be taken in too strict a sense and it should be taken to comprise also an in-situ fluoriding in whlch for at most 20% of the period of in-~itu fluoriding a fluorine slip occurs that differs from the slip applied during the remaining period, which slip has a fixed value (SF). The average fluorine slip SA is given by the formula ~ S .(~t) SA t ~ where Sn is the constant fluorine 81ip over a period (At) and t is the total duration of time of the process of in-situ fluoriding. For the theoretical case where in an in-situ fluoriding with application of a constant fluorine slip the fluorine slip has the fixed value SF throughout the in-situ fluoriding, SG i3 naturally equal to SF.
(b) The temperature gradient (G) should be at most 30 C and the product f SA (in %w) and G (in C) should be at mo~t 1000. The temperature gradient is defined as the temperature difference between the end and the beginninE of the catalyst bed.If the catalyst is dis-tributed over several beds the temperature gradient should be taken to mean the temperature difference between the end of the ~678~30 last bed a~d the beginning of the fir3t bed.
(c~ If a constant fluorine 81ip which on a~erage amount~ to less than 50 %w is used, for a uniform distribution Or fluorine over the catalyst bed to be obtained it is nece~sary to use a temperature gradient as well. This temperature gradient should be at least 300/sA ir SA is less than 40 %w and should be at least 3/ll ~50-SA) if SA is at least 40 %w and less than 50 ~w.
(d) If a constant fluorine slip which on average amount~ to at least - 50 %w is used, application of a temperature gradient in order to obtain a uniform distribution of fluorine over the catalyst bed may be omitted.
In this patent application, by a uniform distributîon of Pluorine over the catalyst bed is meant a distribution of fluorine in which the quotient Or the fluorine content of the catalyst at the end of the catalyst bed (F2) and the fluorine content of the catalyst at the beginning of the catalyst bed (F1~ may vary between 0.5 and 1.5.
In the practical application of in-situ fluoriding using a fluorine slip, it is desirable, to keep the fluorine slip as small ~s possible, inter alia for the ~ollowing four reason~. First, from the point o~
view of rluorine utilization it is desirable that as much as possible of the fluorine fed to the reactor should actually be emplaced on the catalyst. Secondly, ir the quantity of fluorine ~ed to the reactor per unit time remains the same, the time required for the in-situ fluoriding will be shorter according as a smaller fluorine slip i9 applied, Thirdly, the reaction product will contain less fluorine according as a smaller fluorine slip is applied. Finally, it i.9 desirable from the point of view of possible corrosion that as little fluorine as possible comes into the equipment a~ter the reactor. With respect to the arguments put forward under secondly and thirdly it may be observed that these are especially important when the in~situ ~luoriding is 1~67~38~
carried out in the initial stage Or the process for which the catalyst is used. For3 during the in-situ fluoriding the properties of the catalyst will be chan~ing and so will the properties of the product discharged during this period. It is therefore desirable to keep this period as short as possible. In addition, all the fluorine that is not absorbed by the catalyst comes into the product and has to be removed from it. This is another reason why it is important that the largest possible proportion of the fluorine fed to the reactor should be left behind in the catalyst.
An unfortunate circumstance in this connection is, however, the above-mentioned requirement, according to which a small constant fluorine slip should always be accompanied by a positive temperature gradient whose minimum value should be larger according as the fluorine slip applied is smaller. In fact, it has been found that the generation of a temperature gradient through the catalyst bed and its maintenance throughout the in-situ fluoriding are difficult to realize in processing on a technical scale and become even more difficult according as Q
larger temperature gradient is required. This is cau~ed by the fact that reactors meant ~or operation on a technical scale are generally ~o constructed that no heat can be supplied to the process or removed from it via the reactor wall. The facts given hereinbefore imply that the proce3s mentioned above9 in which use is made of a constant ~luorine slip between 10 and 50 5w~ which process can be reali2ed without difficulty on a laboratory or on a semi-technical scale, will meet with serious problems when applied on a technical scale.
It has been found that in the in-situ fluoriding with the use of a fluorine slip between 10 and 50 %w, a uniform distribution of Muorine over the catalyst b0d caIl be obtained without the need o~
also applying a temperature gradient, if instead of a con~tant fluorine sliy a Yariable fluorine 81ip i8 applied. Just as for the proce~s mentioned above, it al~o holds for the latter proce~s that the average slip apnlied should be at least 10 %w. In the lstter proce8~ when ~ v~ri~ble ~06'7~
fluorine slip i8 applied, both in the low 81ip range (10-50 %w) and in the hi6h slip range (> 50 %w) a positive temperature gradient of at most 30C may be applied, if desired. Just as in the process mentioned above, the maximum value of this gradient is again determined by the condition that the product of SA and G should be at most 1000.
If the in-sîtu fluoriding with the use of a constant fluorine slip is defined as a process in which a certain fixed ~luorine slip occurs at leaet 80% of the time, in-situ fluoriding with the u~e of a variable fluorine slip may be defined as a process in which a certain fixed fluorine slip occurs less than 80% of the ti~e.
The present patent application therefore rel~tes to a process ~or the fluoriding of a catalyst, in which process a ~ixed bed of c~t~lyst particlea is fluorided in-situ with the uae of a constsnt or vari~ble fluorine 91ip through the catalyst bed combined or not combined with a positive temperature gradient over the bed, provided that (a) the average fluorlne slip (SA) amounts to at least 10 %w~
(b) the temperature gradient (G) amounts to at mo~t 30C, (c) the product o~ SA (in %w) and G (in C) amounts to at most 1000, (a) a constant fluorine slip which on average ~mounts to less than 40 ~w is accompanied by a temperature gradient of at least 300/SA, and (e) a constant fluorine slip which on average amounts to at least ~0 %w but less than 50 %w is accompanied by a temperature gradient of at least 3/4 (50-SA).
If in the process according to the invention a constant ~luorine slip is used which on average amounta to less than 40 %w, it is pre~erred that it is accompanied by a temp~rature gradient of at lear,t 3/4 (50-SQ).
If a temperature ~radient is used in the procesr, according to the invention, the said aradient should be at mor,t 30 C. I'referQ~ly~ the temperature ~radiel1t should bo lerr, than 25C and ;n t~articu]or ler,s tharl 20C
'-`'`' ~,Q~t7~8~ .
If in the process according to the invention use i8 made of a fluorine slip and, in addition, of a temperature eradient, this temperature gradient should be so chosen that the product of average slip and gradient is at most 1000. Preferably1 in those cases where an average fluorine slip of less than 50 %w i5 used in combination with a temperature gradient, such a temperature 6radient is chosen that the product of average 51ip and gradient is between 400 and 900 and in particular between 500 and 800. In those cases where an average fluorine slip of at least 50 %w is used in combination wi1;h a temperature gradient, it is preferable to choose such a temperature gradient that the product of average slip and gradient is between 100 and ~00, and in particular between 200 and oO0.
The process according to the invention is in general suitable for obtaining a uniform fluorine distribution in the in-situ fluoriding of a fixed bed of catalyst particles. The process is above all of importance for the in-situ fluoriding of a fixed bed of catalyst particles which contain one or more metals having hydrogenative activity, supported on a carrier. Such catalyst3 are used on a large scale in the petroleum industry for the conversion of hydrocarbon fractions in the presence of hydrogen. For this purpose it is preferred to use catalysts which contain one or more metals chosen from Groups VI B, YII B and VIII
of the Periodic System, supported on a carrier. As catalytically active metal component the catalysts may contain both one or more noble metals and one or more base metals. Catalysts having as catalytically active metal component one or more noble metals generally contain 0.5-5 parts by weight and preferably 0,1-2 parts by weight of metal per 100 parts by weight of carrier. Very suitable noble metals are palladium and platinum. The catalysts which contain as catalytically active metal component one or more noble metals are preferably used in reduced form.
Catalysts having as catalytically active metal component a base metal or a combination of base m.tals, generally contain 1-150 parts by ~0678~3~
weigh~ of metal per 100 parts by weight Or carrier. The quantity of metal which must be present on these catalysts is to a large extent determined by the nature of the process for which the catalyst is intended.
Very suitable metal combinations consist of one or more metals of Groups VIB and VIIB and, in addition, one or more metals from the iron group;
particularly suitable are combinations which contain molybdenum and/or tungsten and, in addition, nickel and/or cobalt. The catalysts which contain as catalytically active metal component one or more base metals are preferably used in sulphided form. Suitable carriers for the present catalysts are both amorphous and crystalline materials. Exa~ples of amorphous carriers are oxides of the elements from groups II, III
and IV of the Periodic System, such as silica, alumin~, magnesia, ~irconia and mixtiIres of these oxides such as silica-alumina and silica-z;rconia.
Examples of crystalliné carriers are zeolites, such as fauJasite. If de~ired, mixtures of Emorphous and crystalline materials may also be used as carriers.
The quantity of fluorine applied to the catalysts in the proce~s according to the invention may vary within wide limits, depending inter alia on the catalytically active metal component which iB present on the catalyst and the purpose for which it is desired to use the catalyst.
If the catalyst contains one or more noble metals, the quantity of fluorine is preferably 0.1-7.5 parts by weight and in particular 0.5-5 parts by weight per 100 parts by weight of carrier material. If the catalyst contains one or more base metals, the quantity of fluorine is preferably 0.5-15 parts by weight and in particular 1-10 part~
by weight per 100 parts by weight of carrier material.
As has been remarked above, the in-situ fluoriding of B CatQly8t is effected by adding, before or during the initial phase of the process in which the catalyst is used~ a suitable fluorine compound to 8, stream of gas and/or liquid which is passed over the catalyst. ~y preference, the in-situ fluoriding Or the catalyst is carried out by addition of a suitable fluorine compound to a stream of liquid which is passed over the catalyst. If the in-situ fluorided catalyst is intended to be used for a liquid feed9 as is generslly the case in the conversion of hydrocarbon fractions, the feed itself can very suitably serve as the stream of liquid to which the fluorine compound is added. If desired, during in-situ fluoriding it is also possible to pa~s another stream of liquid than the feed over the catalyst. If, for example, the in-situ fluorided catalyst is intended to be used in the preparation of light hydrocarbon distillates ~uch as gasoline, by hydrocracking of a heavy hydrocarbon oil such as a flashed distill~te, it is pos~ible to use both the flashed distillate to be converted and a lighter hydrocarbon oil, such as a kerosine or gas oil fraction, as the stream o liquid which is passed over the ca~alyst during in-situ fluoriding. The addition of the fluorine compound to the stream of liquid wh;ch i~ passed over the catalyst is continued until the catalyst has absorbed the requisite quantlty of fluorine~ The fluorine compound may be added as such to the stream of liquid or in the form of a concentratP, for example in a lieht hydrocarbon ~raction. It is pre~erred to use an organic fluorine compound as fluoriding agent. Examples of suitable organic fluorine compoùnds for this purpose are orthofluorotoluene and difluoroethane.
The conditions under which the in-situ fluoriding according to the invention is carried out may vary within wide limits, dependent, inter alia, on the nature of the fluoriding agent used, the type of catalyst, the nature of the stream of liquid which i5 passed over the catalyst and the average fluorine slip desired. Suitable conditions for carrying out the in-situ fluoriding according to the invention are a temperature of 100-400C, a pressure of 5-200 bar, a space velocity of 0.5-5 litres of stream of liquid per litre of catalyst per hour and a hydrogen/stream of li~uid ratio of 200-2000 Nl/l.
The total quantity of fluorine to be added to the ~tream of liquid during in-~itu fluoridine depends on the quantity of catalyst ta be ~ ;7~30 fluorided, the requi~ite fluorine content of the catalyst and the average fluorine slip used. The in-situ fluoridin~ is pre~erably carried out by continuously adding a fluorine compound to the liquid which is passed over the catQlyst~ until the calculated total quantity of fluorine has been added. At a given space velocity, the time required for the introduction of a given quantity of fluorine into the catalyst depends on the used concentration of the fluorine compound in the liquid and on the average fluorine slip used. The higher the concentration of the fluorine compound in the liquid and the smaller the average fluorine slip, the shorter the time required for tbe in-situ fluoriding.
During in-situ fluoriding o~ the catalyst, preferably a quantity of 20-2000 ppmN and in particular of 50-1000 ppmw of fluorine in the ~orm of a fluorine compound is added to the stream of liquid.
As has been explained above, an average fluorine slip of a~ least 10% by weight should be used in the method according to the invention.
The quantity of fluorine which is not absorbed by the catalyst depends on the nature of the fluoriding agent used and on the nature of the catalyst to be fluorid~d and further on the reaction conditions used during in-situ fluoriding and on the nature of the liquid which is passed over the catalyst. As a general rule, for a eiven fluoriding agent and cstalyst the fluorine slip will be larger according as the in-situ fluoriding is carried out at a l~wex temperature and pressure and a higher space velocity and according as the liquid which iB passed over the catalyst has a highex nitrogen and aromatic content. Consequently, for a given fluoriding agent, catalyst and liquid which is passed over the catalyst, it is possible by means of a number o~ simple experiments to determine the fluorine slip occurring under certain reaction conditions and subsequently determine how the reaction conditions should be modified in order to achieve a desired slip.
A variaDle ~luorine slip in the process according to the invention can be realized at reaction conditions that otherwise remain the same, 0~8~(~
~ 1 inter alia by varying the quantity Or fluorine that is supplied to the catalyst per unit time during the in-situ fluoriding. An increa3e in the quantity o~ ~luorine supplied to the catalyst causes the fluorine slip to increase, whereas a decrease in the quantity of fluorine supplied to the catalyst causes the fluorine slip to diminish. A variation of the quantity of fluorine that is supplied to the catalyst during the in-situ fluoriding per unit time can be achieved by increasing or decreasing the concentration of the fluorine compo~nd in the liquid that is passed over the catalyst. A variation of the quantity o~ fluorine that is supplied to the catalyst during the in-situ fluoriding per unit time can also be achieved by recycline at least part of a ~luorine-containing gaæ
phase separatea from the reaction product. The ~luorine 81ip i8 higher according as more gas with a hi~her fluorine content is recycled. A
variable fluorine slip can also be realized during the in-situ fluoriding by varyine the reaction conditions and/or the composition of the liquid that is passed over the catalyst while the qusntity of ~luorine that is supplied per unit time to the cstalyst is kept constant. An increase o~ the temperature and/or the pressure and/or a decrease of the space v~locity andtor the nitrogen content andlor the aromatics content of the liquid that is passed over the catalyst reduces the fluorine ~lip, whereas a decrease o~ the temperature and/or the pressure and/or an increase of the space velocity and/or the nitrogen content and/or the aromatics content of the liquid that is passed over the catalyst causes the fluorine slip to increase.
If in the process according to the invention use is made o~ à
fluorine slip and, in addition, of a temperature gradient, this temper~ture gradient must be positive, i.e. the temperature at the end of the catalyst bed must be higher than that at the beginning of the catalyst bed and moreover the tem~erature o~ the catalyst should display a uniform rise alone the direction of flow of the feed through the bed. The temperature gradient should be at most 30 C.
~L~67~30 The desired temperature gradient may be effected in the process according to the invention in various manners, according to the conditions under which the in-situ fluoriding is carried out. In general it may be stated that the desired temperature gradient either occurs as such during the in-situ fluoriding or has to be set by the addition of heat to the catalyst bed or by the removal of heat from the catalyst bed.
This mc~y be explained in more detail as follows. As has been stated above, when using~ for example, the in-situ fluorided catalyst for the conversion of a flashed distillate into gasoline by hydrocracking~
it is possible to use as liquid which is passed over the catalyst durine the in-situ fluoriding,both the flashed distillate to be converted and a kerosine fraction. Since the quantity of heat generated when carrying out in-situ fluoriding under mild conditions is generally fairly small, heat will have to be supplied to the catalyst bed5 particularly if a fairly strong temperature gradient is desired. The most severe conditions are under which the in-situ fluoricling is carried out, the more heat there will be generated and situations may occur in which the desired temperature gradient occurs as such or in which even so much heat is generated that heat has to be removed ~rom the catal~st bed in order to maintain the desired temperature gradientO The three above-mentioned possibilities can occur both if kerosine is used as liquid which is passed over the catalyst during the in-situ fluoriding and if flashed distillate to be converted is used for this purpose.
A special situation can also occur if during the in-situ fluoriding the flashed distillate is used as the liquid which is passed over the catalyst and if the conditions during in-situ fluoriding are so chosen that even at this stage some of the feed i8 already converted by hydrocracking.
~s more cracking occurs, so more heat will be generated and consequently more heat will have to be removed from the catalyst bed in order to maintain the desired temperaturé gradient.
106~7~38(~
;
The process according to the invention is very suitable to be used for in-situ ~luoriding of catalysts which contain one or more metals having hydrogenative activity and supported on a carrier, when using these catalysts for the conversion Or hydrocarbon fractions at elevated temperature and pressure and in the presence of hydrogen.
Examples of such processes in which in-situ fluorided catslysts according to the invention are pre~erably used are as follows:
1. The hydrocracking of heavy hydrocarbon oils, such as flashed distillate for the preparation of light hydrocarbon distillates such AS gasolines and kerosines.
The invention relates to a process for the fluoriding of a catalyst.
For a number of catalytic processes, the suitability of the catalyst can be improved by incorpo~ting fluorine therein. Incorporation of fluorine in catalysts can basically be effected in two manners. Fluorine can be incorporated in the catalysts during their preparation, for example by impregnation of the carrier with a suitable fluorine compound. It is also possible to ineorporate fluorine in the finished catalyst prior to or during the initial phase of the process for which the catalyst is utilized, by addition of a sl~ table fluorine compound to a stream of gas and/or liquid which is passed over the catalyst. If desired, the latter fluoridin~ technique, which is generally referred to as in-s1tu fluoriding, may be combined with the impregnation technique mentioned before.
Durin~ in-situ fluoriding, fluorine produced by dec~mposition of the utilized fluorine compound under the prevailing reaction conditions i~ absorbed by the catalyst. In practice, the in-situ fluoriding process is continued until the catalyst has absorbed the calculated quantity of` fluorine. In this case the conditions are so chosen that rirtually sll the fluorine supplied to the catalyst is in fact absorbed thereby.
During an investigation carried out by the Applicant into the in-situ f`luoriding of a fixed bed of catalyst particles, it has been established that the above-described technique as a rule leads to a non-uniform distribution of fluorine over the catalyst bed, with an excess of fluorine in the first part of the bed and a deficiency thereof in the final part of the bed. In processes where optimum eatalyst perforrnance is dependent on a given minimum quantity of fluorine on the catalyst, a non-uniform distribution of fluorine over the eatalyst bed eauses no harm, provided that the requisite minimum quantity of fluorine is present throu~hout the catalyst bed. In most eases, however, optimum eatalyst performance is dependent on a given fixed fluorine eontent and the perrormance of the catalyst is worse if its fluorine '7~
!
content is above or below that fixed level.
It has been found that during the in-situ fluoriding of a fixed bed of catalyst particles a uniform dis~ribution of fluorine over the bed can be obtained if use is ~ade of a constant fluorine slip throu~h the bed combined or not combined with a positive temperature gradient over the bed, the conditions to be met being as follows:
(a) '~he average fluorine slip (SA) should be at least 10 %w. A fluorine slip is de~ined as the percentage by weight of the supplied quantity of fluorine which is not absorbed by the catalyst bed. Because of the fact that during the initial and the final stage of the in-situ f fluoriding, as well as, to a lesser degree, during the course of the in-situ fluoriding fluctuations in the fluorine slip cannot be avoided, the concept of "in-situ fluoriding with the use of a con3tant fluorine slip" should not be taken in too strict a sense and it should be taken to comprise also an in-situ fluoriding in whlch for at most 20% of the period of in-~itu fluoriding a fluorine slip occurs that differs from the slip applied during the remaining period, which slip has a fixed value (SF). The average fluorine slip SA is given by the formula ~ S .(~t) SA t ~ where Sn is the constant fluorine 81ip over a period (At) and t is the total duration of time of the process of in-situ fluoriding. For the theoretical case where in an in-situ fluoriding with application of a constant fluorine slip the fluorine slip has the fixed value SF throughout the in-situ fluoriding, SG i3 naturally equal to SF.
(b) The temperature gradient (G) should be at most 30 C and the product f SA (in %w) and G (in C) should be at mo~t 1000. The temperature gradient is defined as the temperature difference between the end and the beginninE of the catalyst bed.If the catalyst is dis-tributed over several beds the temperature gradient should be taken to mean the temperature difference between the end of the ~678~30 last bed a~d the beginning of the fir3t bed.
(c~ If a constant fluorine 81ip which on a~erage amount~ to less than 50 %w is used, for a uniform distribution Or fluorine over the catalyst bed to be obtained it is nece~sary to use a temperature gradient as well. This temperature gradient should be at least 300/sA ir SA is less than 40 %w and should be at least 3/ll ~50-SA) if SA is at least 40 %w and less than 50 ~w.
(d) If a constant fluorine slip which on average amount~ to at least - 50 %w is used, application of a temperature gradient in order to obtain a uniform distribution of fluorine over the catalyst bed may be omitted.
In this patent application, by a uniform distributîon of Pluorine over the catalyst bed is meant a distribution of fluorine in which the quotient Or the fluorine content of the catalyst at the end of the catalyst bed (F2) and the fluorine content of the catalyst at the beginning of the catalyst bed (F1~ may vary between 0.5 and 1.5.
In the practical application of in-situ fluoriding using a fluorine slip, it is desirable, to keep the fluorine slip as small ~s possible, inter alia for the ~ollowing four reason~. First, from the point o~
view of rluorine utilization it is desirable that as much as possible of the fluorine fed to the reactor should actually be emplaced on the catalyst. Secondly, ir the quantity of fluorine ~ed to the reactor per unit time remains the same, the time required for the in-situ fluoriding will be shorter according as a smaller fluorine slip i9 applied, Thirdly, the reaction product will contain less fluorine according as a smaller fluorine slip is applied. Finally, it i.9 desirable from the point of view of possible corrosion that as little fluorine as possible comes into the equipment a~ter the reactor. With respect to the arguments put forward under secondly and thirdly it may be observed that these are especially important when the in~situ ~luoriding is 1~67~38~
carried out in the initial stage Or the process for which the catalyst is used. For3 during the in-situ fluoriding the properties of the catalyst will be chan~ing and so will the properties of the product discharged during this period. It is therefore desirable to keep this period as short as possible. In addition, all the fluorine that is not absorbed by the catalyst comes into the product and has to be removed from it. This is another reason why it is important that the largest possible proportion of the fluorine fed to the reactor should be left behind in the catalyst.
An unfortunate circumstance in this connection is, however, the above-mentioned requirement, according to which a small constant fluorine slip should always be accompanied by a positive temperature gradient whose minimum value should be larger according as the fluorine slip applied is smaller. In fact, it has been found that the generation of a temperature gradient through the catalyst bed and its maintenance throughout the in-situ fluoriding are difficult to realize in processing on a technical scale and become even more difficult according as Q
larger temperature gradient is required. This is cau~ed by the fact that reactors meant ~or operation on a technical scale are generally ~o constructed that no heat can be supplied to the process or removed from it via the reactor wall. The facts given hereinbefore imply that the proce3s mentioned above9 in which use is made of a constant ~luorine slip between 10 and 50 5w~ which process can be reali2ed without difficulty on a laboratory or on a semi-technical scale, will meet with serious problems when applied on a technical scale.
It has been found that in the in-situ fluoriding with the use of a fluorine slip between 10 and 50 %w, a uniform distribution of Muorine over the catalyst b0d caIl be obtained without the need o~
also applying a temperature gradient, if instead of a con~tant fluorine sliy a Yariable fluorine 81ip i8 applied. Just as for the proce~s mentioned above, it al~o holds for the latter proce~s that the average slip apnlied should be at least 10 %w. In the lstter proce8~ when ~ v~ri~ble ~06'7~
fluorine slip i8 applied, both in the low 81ip range (10-50 %w) and in the hi6h slip range (> 50 %w) a positive temperature gradient of at most 30C may be applied, if desired. Just as in the process mentioned above, the maximum value of this gradient is again determined by the condition that the product of SA and G should be at most 1000.
If the in-sîtu fluoriding with the use of a constant fluorine slip is defined as a process in which a certain fixed ~luorine slip occurs at leaet 80% of the time, in-situ fluoriding with the u~e of a variable fluorine slip may be defined as a process in which a certain fixed fluorine slip occurs less than 80% of the ti~e.
The present patent application therefore rel~tes to a process ~or the fluoriding of a catalyst, in which process a ~ixed bed of c~t~lyst particlea is fluorided in-situ with the uae of a constsnt or vari~ble fluorine 91ip through the catalyst bed combined or not combined with a positive temperature gradient over the bed, provided that (a) the average fluorlne slip (SA) amounts to at least 10 %w~
(b) the temperature gradient (G) amounts to at mo~t 30C, (c) the product o~ SA (in %w) and G (in C) amounts to at most 1000, (a) a constant fluorine slip which on average ~mounts to less than 40 ~w is accompanied by a temperature gradient of at least 300/SA, and (e) a constant fluorine slip which on average amounts to at least ~0 %w but less than 50 %w is accompanied by a temperature gradient of at least 3/4 (50-SA).
If in the process according to the invention a constant ~luorine slip is used which on average amounta to less than 40 %w, it is pre~erred that it is accompanied by a temp~rature gradient of at lear,t 3/4 (50-SQ).
If a temperature ~radient is used in the procesr, according to the invention, the said aradient should be at mor,t 30 C. I'referQ~ly~ the temperature ~radiel1t should bo lerr, than 25C and ;n t~articu]or ler,s tharl 20C
'-`'`' ~,Q~t7~8~ .
If in the process according to the invention use i8 made of a fluorine slip and, in addition, of a temperature eradient, this temperature gradient should be so chosen that the product of average slip and gradient is at most 1000. Preferably1 in those cases where an average fluorine slip of less than 50 %w i5 used in combination with a temperature gradient, such a temperature 6radient is chosen that the product of average 51ip and gradient is between 400 and 900 and in particular between 500 and 800. In those cases where an average fluorine slip of at least 50 %w is used in combination wi1;h a temperature gradient, it is preferable to choose such a temperature gradient that the product of average slip and gradient is between 100 and ~00, and in particular between 200 and oO0.
The process according to the invention is in general suitable for obtaining a uniform fluorine distribution in the in-situ fluoriding of a fixed bed of catalyst particles. The process is above all of importance for the in-situ fluoriding of a fixed bed of catalyst particles which contain one or more metals having hydrogenative activity, supported on a carrier. Such catalyst3 are used on a large scale in the petroleum industry for the conversion of hydrocarbon fractions in the presence of hydrogen. For this purpose it is preferred to use catalysts which contain one or more metals chosen from Groups VI B, YII B and VIII
of the Periodic System, supported on a carrier. As catalytically active metal component the catalysts may contain both one or more noble metals and one or more base metals. Catalysts having as catalytically active metal component one or more noble metals generally contain 0.5-5 parts by weight and preferably 0,1-2 parts by weight of metal per 100 parts by weight of carrier. Very suitable noble metals are palladium and platinum. The catalysts which contain as catalytically active metal component one or more noble metals are preferably used in reduced form.
Catalysts having as catalytically active metal component a base metal or a combination of base m.tals, generally contain 1-150 parts by ~0678~3~
weigh~ of metal per 100 parts by weight Or carrier. The quantity of metal which must be present on these catalysts is to a large extent determined by the nature of the process for which the catalyst is intended.
Very suitable metal combinations consist of one or more metals of Groups VIB and VIIB and, in addition, one or more metals from the iron group;
particularly suitable are combinations which contain molybdenum and/or tungsten and, in addition, nickel and/or cobalt. The catalysts which contain as catalytically active metal component one or more base metals are preferably used in sulphided form. Suitable carriers for the present catalysts are both amorphous and crystalline materials. Exa~ples of amorphous carriers are oxides of the elements from groups II, III
and IV of the Periodic System, such as silica, alumin~, magnesia, ~irconia and mixtiIres of these oxides such as silica-alumina and silica-z;rconia.
Examples of crystalliné carriers are zeolites, such as fauJasite. If de~ired, mixtures of Emorphous and crystalline materials may also be used as carriers.
The quantity of fluorine applied to the catalysts in the proce~s according to the invention may vary within wide limits, depending inter alia on the catalytically active metal component which iB present on the catalyst and the purpose for which it is desired to use the catalyst.
If the catalyst contains one or more noble metals, the quantity of fluorine is preferably 0.1-7.5 parts by weight and in particular 0.5-5 parts by weight per 100 parts by weight of carrier material. If the catalyst contains one or more base metals, the quantity of fluorine is preferably 0.5-15 parts by weight and in particular 1-10 part~
by weight per 100 parts by weight of carrier material.
As has been remarked above, the in-situ fluoriding of B CatQly8t is effected by adding, before or during the initial phase of the process in which the catalyst is used~ a suitable fluorine compound to 8, stream of gas and/or liquid which is passed over the catalyst. ~y preference, the in-situ fluoriding Or the catalyst is carried out by addition of a suitable fluorine compound to a stream of liquid which is passed over the catalyst. If the in-situ fluorided catalyst is intended to be used for a liquid feed9 as is generslly the case in the conversion of hydrocarbon fractions, the feed itself can very suitably serve as the stream of liquid to which the fluorine compound is added. If desired, during in-situ fluoriding it is also possible to pa~s another stream of liquid than the feed over the catalyst. If, for example, the in-situ fluorided catalyst is intended to be used in the preparation of light hydrocarbon distillates ~uch as gasoline, by hydrocracking of a heavy hydrocarbon oil such as a flashed distill~te, it is pos~ible to use both the flashed distillate to be converted and a lighter hydrocarbon oil, such as a kerosine or gas oil fraction, as the stream o liquid which is passed over the ca~alyst during in-situ fluoriding. The addition of the fluorine compound to the stream of liquid wh;ch i~ passed over the catalyst is continued until the catalyst has absorbed the requisite quantlty of fluorine~ The fluorine compound may be added as such to the stream of liquid or in the form of a concentratP, for example in a lieht hydrocarbon ~raction. It is pre~erred to use an organic fluorine compound as fluoriding agent. Examples of suitable organic fluorine compoùnds for this purpose are orthofluorotoluene and difluoroethane.
The conditions under which the in-situ fluoriding according to the invention is carried out may vary within wide limits, dependent, inter alia, on the nature of the fluoriding agent used, the type of catalyst, the nature of the stream of liquid which i5 passed over the catalyst and the average fluorine slip desired. Suitable conditions for carrying out the in-situ fluoriding according to the invention are a temperature of 100-400C, a pressure of 5-200 bar, a space velocity of 0.5-5 litres of stream of liquid per litre of catalyst per hour and a hydrogen/stream of li~uid ratio of 200-2000 Nl/l.
The total quantity of fluorine to be added to the ~tream of liquid during in-~itu fluoridine depends on the quantity of catalyst ta be ~ ;7~30 fluorided, the requi~ite fluorine content of the catalyst and the average fluorine slip used. The in-situ fluoridin~ is pre~erably carried out by continuously adding a fluorine compound to the liquid which is passed over the catQlyst~ until the calculated total quantity of fluorine has been added. At a given space velocity, the time required for the introduction of a given quantity of fluorine into the catalyst depends on the used concentration of the fluorine compound in the liquid and on the average fluorine slip used. The higher the concentration of the fluorine compound in the liquid and the smaller the average fluorine slip, the shorter the time required for tbe in-situ fluoriding.
During in-situ fluoriding o~ the catalyst, preferably a quantity of 20-2000 ppmN and in particular of 50-1000 ppmw of fluorine in the ~orm of a fluorine compound is added to the stream of liquid.
As has been explained above, an average fluorine slip of a~ least 10% by weight should be used in the method according to the invention.
The quantity of fluorine which is not absorbed by the catalyst depends on the nature of the fluoriding agent used and on the nature of the catalyst to be fluorid~d and further on the reaction conditions used during in-situ fluoriding and on the nature of the liquid which is passed over the catalyst. As a general rule, for a eiven fluoriding agent and cstalyst the fluorine slip will be larger according as the in-situ fluoriding is carried out at a l~wex temperature and pressure and a higher space velocity and according as the liquid which iB passed over the catalyst has a highex nitrogen and aromatic content. Consequently, for a given fluoriding agent, catalyst and liquid which is passed over the catalyst, it is possible by means of a number o~ simple experiments to determine the fluorine slip occurring under certain reaction conditions and subsequently determine how the reaction conditions should be modified in order to achieve a desired slip.
A variaDle ~luorine slip in the process according to the invention can be realized at reaction conditions that otherwise remain the same, 0~8~(~
~ 1 inter alia by varying the quantity Or fluorine that is supplied to the catalyst per unit time during the in-situ fluoriding. An increa3e in the quantity o~ ~luorine supplied to the catalyst causes the fluorine slip to increase, whereas a decrease in the quantity of fluorine supplied to the catalyst causes the fluorine slip to diminish. A variation of the quantity of fluorine that is supplied to the catalyst during the in-situ fluoriding per unit time can be achieved by increasing or decreasing the concentration of the fluorine compo~nd in the liquid that is passed over the catalyst. A variation of the quantity o~ fluorine that is supplied to the catalyst during the in-situ fluoriding per unit time can also be achieved by recycline at least part of a ~luorine-containing gaæ
phase separatea from the reaction product. The ~luorine 81ip i8 higher according as more gas with a hi~her fluorine content is recycled. A
variable fluorine slip can also be realized during the in-situ fluoriding by varyine the reaction conditions and/or the composition of the liquid that is passed over the catalyst while the qusntity of ~luorine that is supplied per unit time to the cstalyst is kept constant. An increase o~ the temperature and/or the pressure and/or a decrease of the space v~locity andtor the nitrogen content andlor the aromatics content of the liquid that is passed over the catalyst reduces the fluorine ~lip, whereas a decrease o~ the temperature and/or the pressure and/or an increase of the space velocity and/or the nitrogen content and/or the aromatics content of the liquid that is passed over the catalyst causes the fluorine slip to increase.
If in the process according to the invention use is made o~ à
fluorine slip and, in addition, of a temperature gradient, this temper~ture gradient must be positive, i.e. the temperature at the end of the catalyst bed must be higher than that at the beginning of the catalyst bed and moreover the tem~erature o~ the catalyst should display a uniform rise alone the direction of flow of the feed through the bed. The temperature gradient should be at most 30 C.
~L~67~30 The desired temperature gradient may be effected in the process according to the invention in various manners, according to the conditions under which the in-situ fluoriding is carried out. In general it may be stated that the desired temperature gradient either occurs as such during the in-situ fluoriding or has to be set by the addition of heat to the catalyst bed or by the removal of heat from the catalyst bed.
This mc~y be explained in more detail as follows. As has been stated above, when using~ for example, the in-situ fluorided catalyst for the conversion of a flashed distillate into gasoline by hydrocracking~
it is possible to use as liquid which is passed over the catalyst durine the in-situ fluoriding,both the flashed distillate to be converted and a kerosine fraction. Since the quantity of heat generated when carrying out in-situ fluoriding under mild conditions is generally fairly small, heat will have to be supplied to the catalyst bed5 particularly if a fairly strong temperature gradient is desired. The most severe conditions are under which the in-situ fluoricling is carried out, the more heat there will be generated and situations may occur in which the desired temperature gradient occurs as such or in which even so much heat is generated that heat has to be removed ~rom the catal~st bed in order to maintain the desired temperature gradientO The three above-mentioned possibilities can occur both if kerosine is used as liquid which is passed over the catalyst during the in-situ fluoriding and if flashed distillate to be converted is used for this purpose.
A special situation can also occur if during the in-situ fluoriding the flashed distillate is used as the liquid which is passed over the catalyst and if the conditions during in-situ fluoriding are so chosen that even at this stage some of the feed i8 already converted by hydrocracking.
~s more cracking occurs, so more heat will be generated and consequently more heat will have to be removed from the catalyst bed in order to maintain the desired temperaturé gradient.
106~7~38(~
;
The process according to the invention is very suitable to be used for in-situ ~luoriding of catalysts which contain one or more metals having hydrogenative activity and supported on a carrier, when using these catalysts for the conversion Or hydrocarbon fractions at elevated temperature and pressure and in the presence of hydrogen.
Examples of such processes in which in-situ fluorided catslysts according to the invention are pre~erably used are as follows:
1. The hydrocracking of heavy hydrocarbon oils, such as flashed distillate for the preparation of light hydrocarbon distillates such AS gasolines and kerosines.
2. The preparation of high-viscosity-index lubricating oils by means of a catalytic hydrogen treatrnent of heavY hydrocarbon oils such as deasphalted oils and oil~containing paraffin mixtures.
3. The b~drogeDation of aromatics present in light hydrocarbon oil distillates, such as kerosines.
4. The hydroisomerization or hydrocracking of unbranched paraffins present in light hydrocarbon oil distillates in order to increase ; the octane number of these distillates.
The inYention will now be elucidated with reference to the following examples.
EXAMPLE I
Starting from six catalyst base materials (A-F), 13 difPerent catalysts were prepared by in-situ fluoriding. The in-situ fluoriding was carried out by passing a liquid, to which a certain quantity of a fluorine compound had been added, for a given time at elevated temperature and pressure and in the presence of hydrogen, over a catalyst base material which was present in the form of a fixed bed in a cylindrical reactor. The liquids used were two heavy gas oils (HGO and HGO~), a deasphalted residual hydrocarbon oil (DAO) and a kerosine (KER).
The fluorine compounds used were 1,1-difluoroethane (DFE) and ortho-fluoro-~067~
- 14 _ toluene (OFT~. In all cases except for experiments 8 and 13 a constant fluorine ~lip through the bed was used either combined or not combined with a positive temperature gradient over the bed. The in-situ fluoriding was continued until the catalyst had absorbed the desired quantity of fluorine. On completion of the in-situ fluoriding, the fluorine content at the beginning of the catalyst bed (F1) and the fluorine content at the end of the catalyst bed (F2) was determined. The composition of the catalyst base materials A-F is stated in Table I. Some properties of the liquids used are stated in Table II. The conditions under which the in-situ fluoriding experiments were carried out are ~tated in Table III, together with the value measured for Fl and F2.
Table I
Catalyst base C~mpo~ition, parts by wt per 100 parts material, No. by wt of alumina carrier Nlckel Molybdenum OE~g ten ~ospfiorus ____________ ______ __________ ___ __~_ ___________ A 3.8 16.0 _ 4.0 11.0 18.0 C 4.2 17.7 - 2.8 D 4.1 16.8 - 4.2 E 5.0 _ 30.0 F10.0 - 60.0 ==_===_,============================_=======_========__=
Table II
Liquid which is pa~sed over Nitrogen content Poly(>tri)aromatic the catalyst base material of the liquid, content in during in-situ fluoriding ppmw molj100 g __________.. ___ ___._________ ________________ __________~_______ ~GO 160 9 TIGO* 200 11 Dl~O 640 35 ===============================_===============~===a==========~~=
~1:36788ai - 1s-o ~ o o U~ ~ o ~ ~ o _ O O ~D . O ~ ~
~ o o ~ ~ o U~ ~ o O E~ O u~ u~ 0 o . 0 ~ ~ ~ ~ 1 o ~ ~ . o ~ . ~ .
o o ~ ~ o U~ .
~ . , .
~; O O0 0 0 0 0 0 C\l t-- I
-- ') ~ O N ~ ~ ~) ~; O u~ N -- O ~ I
--O O O 0 OU~ N 1 0 O ¢~Fs~ O O~ ~ O ~ ~
`~; O ~ O . U~ I
O
O1:~:1 0 u~ O O o'~ o O . O
OE~ O u~ O U~ I O
0 C~ . O t-- ~ O ~ ~ ~ O
~O ~ t~ -O U~ I
O
OE`~ O JIf~ 0 0 u~ N ~
O t--~) O u~ N
O 1:~ 0 O~ O o o u~ ~ 3 O N ~D~ O
O 11~ 0 0 0 -- O I N
0 o ~.:t o.
H ~ N -- _ O
H ~
~ O ~ O O U~O O ~ -- O ~ 0 ,D ~ C~ O O ~O O ~ ~
E~ _ ~ O
O -- U~ 0 g _ ~ o o~
~ o t- ~) ~ o U~ ~ ~ i ~ o c~ g N 1~ 0 _ N -- ~
~ OO~ ~ -- O , U~ ~ . _ I
I
o ~O ~ O -- ~ N ~ :
h o a O~ ~D " O
~i r1 n ~ E;~ rl ~ O ~ 1~4 ~ I
r-l ~ P~ ~1 rl Id ~
rl rl ql u~ O-- O ~ rl h ~ ~ h o ~ r~ s r-l s~ h r~ S~ 0 ~3 r~
D CJ~ I r~ r~ ~ rJ ~ r~
R l LI 111 r-l O I rl bD ~ h sl Id ~ Q) ~ h I
~ ~ h t~l ~ r-l 1 ~ (d ~ ~ bhD ~ ~ ~0 ~ ~ I
u~ ~ a ~ P o P~ o a (~ u O r~ ~ t~ 4 ~ z ~ a) ~ S ~ O co $
a I
X : ~ ~ r1 rl I ~ I h r1 ~ 8 ~ i --1 ri h h ~J rl u~ h bD ~ O h t) ~q _ r-i I
0 ~ O O C~ rcl ~: rl :~ O ~ O v td p~ O h a) ~ ~ rl llJ El ~ h d rl r-i r-l O rl ~ r-l r;1 p 1~ r-l 1 0 ~
rl c~ E~ ~ Pl P~ O I
78~(~
0~ the in-situ fluoriding experiments 1-13 stated in Table III, only experimenta 1-5 were carried out according to the invention. Experiments 6-13 fall outside the scope of the present patent application and are included for the purpose of comparison.
In experiments 1, 2 and 4 an average slip of between 10 and 40 %w was used in combination with a gradient below 30 C, which gradient met the requirement 300/S~_G~1000. III experiment 3 an average slip of between 40 and 50 ~w was used in combination with a gradient below 30C, which gradient met the requirement 3/4(50-SA)~G<1000. In experiment 5 an average slip in excess of 50 %w was used without temperature gradient. In each of experiments 1-5 a uniform distribution of fluorine over the catalyst bed was obtained, featured by a quotient F2/F1 of between 0.5 and 1,5.
In experiment 6 and 10 an average slip smaller than 10 %w was used. In experiment 7 a gradient above 30 C was used. Experiments 8 and 13 were carried out without a 91ip. In experiment~ 9 and 11 the product of slip and gradient was above 1000. In experiment 12 an average 8~ip between 10 and 40 %w was used in combination wqth a gradient, but this gradient did not meet the requirement G>300/SAo In each of the experiments 6-13 a non-uniform distribution of fluorine w er the catalyst bed was obtained, featured by a quotient F2/F1 of above 1.5 or below 0.5, EXAMPLE II
'rhe in-situ fluoriding experiments 1 and 6 described in Example I were carried out on a fixed bed of catalyst base material B. In both e'xperiments, on completion of the in-situ fluoriding the catalyst bed had an average fluorine content of 2.8 parts by weight per 100 parts by weight of alumina carrier. Both the in-situ fluorided catalyst beds ~rere used ~n separate experiments for the preparation of lubr;cating oil t)y hydrocracking of an oi]-containing ~araffin mixture.
~67~
The paraffin mixture had the following properties:
VX (kinematic viscosity at 210 ~): 14.99 cSt Sulphur content : 0.32 %w Nitrogen content : 34 ppmw Oil content (determined by dewaxing a' -30 C with a mixture of methyl ethyl ketone and toluene) : 34.2 ~w Hydrocracking of the oil-containing paraffin mixture was effected at a total pressure of 140 bar, a space velocity of 1.0 kg.l .h 7 a hydrogen/feed ratio of 1500 NlH2/kg of feed and such a tem~?erature that a paraffin converæion of 65% occurred (by paraffin conversion is meant in this context:
%w of paraffins in feed - %w of-~,araffins in 390C product %w oP paraffins in feed x 100%) The hydrocracked product was topped off at 390 C and the 390C
fraction was dewaxed at -30C with a mixture of methyl ethyl ketone and toluene~ The results of the two hydrocracking experiments are stated in Table IV.
Table IV
:
Using the catalyst bed fluorided in-situ according to exp. No.
_______________________ _ _ _ _ _ _ _ _ _ _ Requisite temp. for reaching a paraffin conversion of 65%, C 383 390 Yield of dewaxed 3~0C lubri cating oil based on feed, %w 40 36 Vk210 of the dewaxed lubricating 7.7 7.1 oil cSt =========================================================
The results stated in Table IV demonstrate clearly the great importance of a uniform distribut;on of fluorine over the catalyst bed (0.5 ~ F2/F1 ~ 1.5).
Although both the ca-talyst beds have the same fluorine content of 2.8 parts by weight per 100 parts by wei~;ht of alumina carrier, the catalyst bed fluorided in-situ according to the invention (cf. experiment 1 with F2/F~ = 0.7~) is capable at a lowe^ temperature of giving a higher yield ol lu~ricatine oil with a higher Vk2l0 than the catalyst bed ~.~67~
,~
fluorided in-situ in the conventional manner (cf. experiment 6 wi-th F2/l~'1 = 0.02).
EXAMPLE III
The in-situ fluoriding experiments 3 and 13 described in Example I
were carried out on a ~ixed bed of catalyst base material E. In both experiments, on completion of the in-situ fluoriding the cat~lyst bed had an average fluorine content of 4.1 parts by weight per 100 parts by weight alumina carrier. Both the in-situ fluorided catalyst beds were used in sel.arate-experiments for the preparation of lubricating ail by hydrocracking of the above mentioned deasphalted oil. The de-asphalted oil had the following properties:
Sulphur content: . . . . . . .2.47 %w Nitrogen content:. . . . . . . 640 ppmw Paraffin content:. . . . . . .16.0 %w Hydrocracking of the deasphalted oil was effected at a total pressure of 165 bar, a space velocity of 0.8 kg.l .h , a hydrogenjfeed ratio of 1500 ~lH2/kg and such a temperature that the resulting base oil after topping at 390 C and dewaxing of the 390 C fraction at -30 C
with a mixture of methyl ethylketone and tolue4e had a VIE of about 130.
The results of the two hydrocracking experiments are stated in Table V.
Table V
Vsing the catalyst bed fluorided in-situ according to experiment No ____________ ____________ :
Requisite temperature for ob-taining a dewaxed 390 C+
lubricating oil with a VI of 130, C 402 410 Yield of the dewaxed lubrica-ting oil based on feed, ~w 42 39 The results stated in Table V demorstrate clearly the ereat importance of a 9L~678~3~
,9 .
uniform distribution of fluorine over the catalyst bed (0 5cF2/F1c1 5).
Although both catalyst beds have the same average fluorine content of 4.1 pbw per 100 pbw alumina carrier, the catalyst bed fluorided in-situ accordine to the invention (cf. experiment 3 with F2/F1=1.1) is capable at a lower temperature of giving a hi~her yield of lubricating oil than the catalyst bed fluorided in-situ in the conventional manner (cf. experiment 13 with F2/F1=0.01).
Starting from three catalyst base msterials (G-I), six different catalysts were prepared by in-situ fluoriding. The in-situ fluoriding was carried out by passing a liquid, to which a certain quantity of 1,1-difluoroethane had been added, for a given time at elevated temperature and pressure and in the pre~ence of hydrogen, over the catalyst base material, which was present in the form of a fixed bed in a cylindrical reactor. The liquids used were the heavy g~s oil (~GO*) and the kerosine (KER)described in Table II. In all cases a variable ~luorine slip through the bed was used either combined or not combined with a positive temperature gradient over the bed. The in-situ fluoridine was continued until the catalyst had absorbed the desired quantity of fluorine. On completion of the in-situ fluoriding, the fluorine content at thè beginning of the catalyst bed (F1) and the fluorine content at the end of the catalyst bed (F2) was determined. The composition of the catalyst base materials G-I is stated in Table VI The conditions under which the in-situ fluoriding experiments were carried out are stated in Tables VII and VIII. The values measured for F1 and F2 are also included in Table VII.
The following observations should be made about the conditions at which the in-situ fluoriding experi~ents were carried out.
All the ex~eriments were carried out with gas recycle. To this end the reaction product was cooled to 20-70 C, l;quid and gas were ~ 678l~
separated, the gas was washed or not washed with water and then recycled, The eas, which mainly comprisèd hydrogen~ also contained 1,1-difluoro-ethane, hydrogep sulphide, traces of C4 hydrocarbons and trace~ of am~onia.
In experiments 14, 15 and 18 the temperature was varied durin~
the in-situ fluoriding.
Table VI
Catalyst Composition of the catalyst base Composition of the base ma- material, pb~ per 100 pbw of the carrier pbw per 100 terial, carrier _ _ pbw of the cQrrier - nickel molybde- tunesten pho~pho-. num rus ________ ___---_____ ____________________ G 3.614.3 - 3.5 100 Al203 H 7.8 _ 25.5 ~ 24 SiO2- 76 Al203 I 3.0 - 9 5 - 75 sieve Y - 25 A1203 Table VII
Experiment No. 14 15 16 17 l8 19 Catalyst base materiAl, No. G G G H
: Liquid HG0* HG0* HG0* HG0*KER KER
Fluorine concentration in the liquid, ppmw 300 300 300 300 225 150 . Conditions during the in-situ fluoridin~
Average temp.C 212.5 239 235 235 130 175 Total pressure,bar 130 130 130 130 125 125 Space velocitY, kg l_l.h_l 1.01.0 1.0 1.0 2.0 2,0 :H2/liquid ratio, ~l.kg-1 1000 1000 1000 1000250 1000 Duration of the ex-periment, h 430 250 170 250 542 340 Average fluorine slip,%w 61.5 31.5 35 45 19 9 Temperature gradient,C 15 Fluorine content of the catalyst bed,~ Pbw of fluorine per 100 pb~
-o~ the carrier F1 3.96.1 4.0 4.831.5 11.8 F2 6.66.o 3.~ 4.326.5 5.6 ~6'7~
.
I o U~ ~~ 'I
O j ~l ~ o ,1 O ~ o o 1 "~
!g ' Ei o~
a I O t- ~ NO ~I
!o o,!
I o ~ ~1 ~ o I U~ ~ o U~ "
a I o 1 1 ~ lo ~ o 1, N
u~ ol U~
aE- 19 I o ~ o ~ 11 . I I C~J 'I
~ ~ o 11 E~
1 ~u oD O
,. I
!, ~ ', `" 1l ~ o o 1, O P~ P' h ~ ¦~
~ ~s a,1 o a~ b~ ~ h ~ r/ hO ~ ^ ~ h I
0 ~ bO rOd a ~ ~d ;4i ~d~} h a ,1 bn o 1 O ~) O r~ h P~ J~ ~ C) h ~h) h ~ ~h~ ~ ~h ~ h r~ h 1~
~j~ ~ h ~ ,~H ~d ~ 0 P~ ¦¦
8~30 Of the in-situ fluoriding experiments 14-19 stated in Tables VII and VIII, experiments 14_18 were carried out according to the invention.
Experiment 19 falls outside the scope of the present invention and has been included for comparison.
In experiments 14-18 an average slip above 10 %w was used. Furthermore, in experiments 14 such a gradient below 30C was used that the product of average slip and 6radient was smaller than 1000. In each of experiments 14-18 a uniform distribution of fluorine ~ver the catalyst bed was obtained, characterized by a quotient F2/F1 between 0.5 and 1.5.
In~experiment 19 an average ælip below 10 %w was used. In this experiment a non-uniform distribution of fluorine over the catalyst bed was obtained, characteri~ed by a quotient F2/F1 smaller than P.5.
'~
'
The inYention will now be elucidated with reference to the following examples.
EXAMPLE I
Starting from six catalyst base materials (A-F), 13 difPerent catalysts were prepared by in-situ fluoriding. The in-situ fluoriding was carried out by passing a liquid, to which a certain quantity of a fluorine compound had been added, for a given time at elevated temperature and pressure and in the presence of hydrogen, over a catalyst base material which was present in the form of a fixed bed in a cylindrical reactor. The liquids used were two heavy gas oils (HGO and HGO~), a deasphalted residual hydrocarbon oil (DAO) and a kerosine (KER).
The fluorine compounds used were 1,1-difluoroethane (DFE) and ortho-fluoro-~067~
- 14 _ toluene (OFT~. In all cases except for experiments 8 and 13 a constant fluorine ~lip through the bed was used either combined or not combined with a positive temperature gradient over the bed. The in-situ fluoriding was continued until the catalyst had absorbed the desired quantity of fluorine. On completion of the in-situ fluoriding, the fluorine content at the beginning of the catalyst bed (F1) and the fluorine content at the end of the catalyst bed (F2) was determined. The composition of the catalyst base materials A-F is stated in Table I. Some properties of the liquids used are stated in Table II. The conditions under which the in-situ fluoriding experiments were carried out are ~tated in Table III, together with the value measured for Fl and F2.
Table I
Catalyst base C~mpo~ition, parts by wt per 100 parts material, No. by wt of alumina carrier Nlckel Molybdenum OE~g ten ~ospfiorus ____________ ______ __________ ___ __~_ ___________ A 3.8 16.0 _ 4.0 11.0 18.0 C 4.2 17.7 - 2.8 D 4.1 16.8 - 4.2 E 5.0 _ 30.0 F10.0 - 60.0 ==_===_,============================_=======_========__=
Table II
Liquid which is pa~sed over Nitrogen content Poly(>tri)aromatic the catalyst base material of the liquid, content in during in-situ fluoriding ppmw molj100 g __________.. ___ ___._________ ________________ __________~_______ ~GO 160 9 TIGO* 200 11 Dl~O 640 35 ===============================_===============~===a==========~~=
~1:36788ai - 1s-o ~ o o U~ ~ o ~ ~ o _ O O ~D . O ~ ~
~ o o ~ ~ o U~ ~ o O E~ O u~ u~ 0 o . 0 ~ ~ ~ ~ 1 o ~ ~ . o ~ . ~ .
o o ~ ~ o U~ .
~ . , .
~; O O0 0 0 0 0 0 C\l t-- I
-- ') ~ O N ~ ~ ~) ~; O u~ N -- O ~ I
--O O O 0 OU~ N 1 0 O ¢~Fs~ O O~ ~ O ~ ~
`~; O ~ O . U~ I
O
O1:~:1 0 u~ O O o'~ o O . O
OE~ O u~ O U~ I O
0 C~ . O t-- ~ O ~ ~ ~ O
~O ~ t~ -O U~ I
O
OE`~ O JIf~ 0 0 u~ N ~
O t--~) O u~ N
O 1:~ 0 O~ O o o u~ ~ 3 O N ~D~ O
O 11~ 0 0 0 -- O I N
0 o ~.:t o.
H ~ N -- _ O
H ~
~ O ~ O O U~O O ~ -- O ~ 0 ,D ~ C~ O O ~O O ~ ~
E~ _ ~ O
O -- U~ 0 g _ ~ o o~
~ o t- ~) ~ o U~ ~ ~ i ~ o c~ g N 1~ 0 _ N -- ~
~ OO~ ~ -- O , U~ ~ . _ I
I
o ~O ~ O -- ~ N ~ :
h o a O~ ~D " O
~i r1 n ~ E;~ rl ~ O ~ 1~4 ~ I
r-l ~ P~ ~1 rl Id ~
rl rl ql u~ O-- O ~ rl h ~ ~ h o ~ r~ s r-l s~ h r~ S~ 0 ~3 r~
D CJ~ I r~ r~ ~ rJ ~ r~
R l LI 111 r-l O I rl bD ~ h sl Id ~ Q) ~ h I
~ ~ h t~l ~ r-l 1 ~ (d ~ ~ bhD ~ ~ ~0 ~ ~ I
u~ ~ a ~ P o P~ o a (~ u O r~ ~ t~ 4 ~ z ~ a) ~ S ~ O co $
a I
X : ~ ~ r1 rl I ~ I h r1 ~ 8 ~ i --1 ri h h ~J rl u~ h bD ~ O h t) ~q _ r-i I
0 ~ O O C~ rcl ~: rl :~ O ~ O v td p~ O h a) ~ ~ rl llJ El ~ h d rl r-i r-l O rl ~ r-l r;1 p 1~ r-l 1 0 ~
rl c~ E~ ~ Pl P~ O I
78~(~
0~ the in-situ fluoriding experiments 1-13 stated in Table III, only experimenta 1-5 were carried out according to the invention. Experiments 6-13 fall outside the scope of the present patent application and are included for the purpose of comparison.
In experiments 1, 2 and 4 an average slip of between 10 and 40 %w was used in combination with a gradient below 30 C, which gradient met the requirement 300/S~_G~1000. III experiment 3 an average slip of between 40 and 50 ~w was used in combination with a gradient below 30C, which gradient met the requirement 3/4(50-SA)~G<1000. In experiment 5 an average slip in excess of 50 %w was used without temperature gradient. In each of experiments 1-5 a uniform distribution of fluorine over the catalyst bed was obtained, featured by a quotient F2/F1 of between 0.5 and 1,5.
In experiment 6 and 10 an average slip smaller than 10 %w was used. In experiment 7 a gradient above 30 C was used. Experiments 8 and 13 were carried out without a 91ip. In experiment~ 9 and 11 the product of slip and gradient was above 1000. In experiment 12 an average 8~ip between 10 and 40 %w was used in combination wqth a gradient, but this gradient did not meet the requirement G>300/SAo In each of the experiments 6-13 a non-uniform distribution of fluorine w er the catalyst bed was obtained, featured by a quotient F2/F1 of above 1.5 or below 0.5, EXAMPLE II
'rhe in-situ fluoriding experiments 1 and 6 described in Example I were carried out on a fixed bed of catalyst base material B. In both e'xperiments, on completion of the in-situ fluoriding the catalyst bed had an average fluorine content of 2.8 parts by weight per 100 parts by weight of alumina carrier. Both the in-situ fluorided catalyst beds ~rere used ~n separate experiments for the preparation of lubr;cating oil t)y hydrocracking of an oi]-containing ~araffin mixture.
~67~
The paraffin mixture had the following properties:
VX (kinematic viscosity at 210 ~): 14.99 cSt Sulphur content : 0.32 %w Nitrogen content : 34 ppmw Oil content (determined by dewaxing a' -30 C with a mixture of methyl ethyl ketone and toluene) : 34.2 ~w Hydrocracking of the oil-containing paraffin mixture was effected at a total pressure of 140 bar, a space velocity of 1.0 kg.l .h 7 a hydrogen/feed ratio of 1500 NlH2/kg of feed and such a tem~?erature that a paraffin converæion of 65% occurred (by paraffin conversion is meant in this context:
%w of paraffins in feed - %w of-~,araffins in 390C product %w oP paraffins in feed x 100%) The hydrocracked product was topped off at 390 C and the 390C
fraction was dewaxed at -30C with a mixture of methyl ethyl ketone and toluene~ The results of the two hydrocracking experiments are stated in Table IV.
Table IV
:
Using the catalyst bed fluorided in-situ according to exp. No.
_______________________ _ _ _ _ _ _ _ _ _ _ Requisite temp. for reaching a paraffin conversion of 65%, C 383 390 Yield of dewaxed 3~0C lubri cating oil based on feed, %w 40 36 Vk210 of the dewaxed lubricating 7.7 7.1 oil cSt =========================================================
The results stated in Table IV demonstrate clearly the great importance of a uniform distribut;on of fluorine over the catalyst bed (0.5 ~ F2/F1 ~ 1.5).
Although both the ca-talyst beds have the same fluorine content of 2.8 parts by weight per 100 parts by wei~;ht of alumina carrier, the catalyst bed fluorided in-situ according to the invention (cf. experiment 1 with F2/F~ = 0.7~) is capable at a lowe^ temperature of giving a higher yield ol lu~ricatine oil with a higher Vk2l0 than the catalyst bed ~.~67~
,~
fluorided in-situ in the conventional manner (cf. experiment 6 wi-th F2/l~'1 = 0.02).
EXAMPLE III
The in-situ fluoriding experiments 3 and 13 described in Example I
were carried out on a ~ixed bed of catalyst base material E. In both experiments, on completion of the in-situ fluoriding the cat~lyst bed had an average fluorine content of 4.1 parts by weight per 100 parts by weight alumina carrier. Both the in-situ fluorided catalyst beds were used in sel.arate-experiments for the preparation of lubricating ail by hydrocracking of the above mentioned deasphalted oil. The de-asphalted oil had the following properties:
Sulphur content: . . . . . . .2.47 %w Nitrogen content:. . . . . . . 640 ppmw Paraffin content:. . . . . . .16.0 %w Hydrocracking of the deasphalted oil was effected at a total pressure of 165 bar, a space velocity of 0.8 kg.l .h , a hydrogenjfeed ratio of 1500 ~lH2/kg and such a temperature that the resulting base oil after topping at 390 C and dewaxing of the 390 C fraction at -30 C
with a mixture of methyl ethylketone and tolue4e had a VIE of about 130.
The results of the two hydrocracking experiments are stated in Table V.
Table V
Vsing the catalyst bed fluorided in-situ according to experiment No ____________ ____________ :
Requisite temperature for ob-taining a dewaxed 390 C+
lubricating oil with a VI of 130, C 402 410 Yield of the dewaxed lubrica-ting oil based on feed, ~w 42 39 The results stated in Table V demorstrate clearly the ereat importance of a 9L~678~3~
,9 .
uniform distribution of fluorine over the catalyst bed (0 5cF2/F1c1 5).
Although both catalyst beds have the same average fluorine content of 4.1 pbw per 100 pbw alumina carrier, the catalyst bed fluorided in-situ accordine to the invention (cf. experiment 3 with F2/F1=1.1) is capable at a lower temperature of giving a hi~her yield of lubricating oil than the catalyst bed fluorided in-situ in the conventional manner (cf. experiment 13 with F2/F1=0.01).
Starting from three catalyst base msterials (G-I), six different catalysts were prepared by in-situ fluoriding. The in-situ fluoriding was carried out by passing a liquid, to which a certain quantity of 1,1-difluoroethane had been added, for a given time at elevated temperature and pressure and in the pre~ence of hydrogen, over the catalyst base material, which was present in the form of a fixed bed in a cylindrical reactor. The liquids used were the heavy g~s oil (~GO*) and the kerosine (KER)described in Table II. In all cases a variable ~luorine slip through the bed was used either combined or not combined with a positive temperature gradient over the bed. The in-situ fluoridine was continued until the catalyst had absorbed the desired quantity of fluorine. On completion of the in-situ fluoriding, the fluorine content at thè beginning of the catalyst bed (F1) and the fluorine content at the end of the catalyst bed (F2) was determined. The composition of the catalyst base materials G-I is stated in Table VI The conditions under which the in-situ fluoriding experiments were carried out are stated in Tables VII and VIII. The values measured for F1 and F2 are also included in Table VII.
The following observations should be made about the conditions at which the in-situ fluoriding experi~ents were carried out.
All the ex~eriments were carried out with gas recycle. To this end the reaction product was cooled to 20-70 C, l;quid and gas were ~ 678l~
separated, the gas was washed or not washed with water and then recycled, The eas, which mainly comprisèd hydrogen~ also contained 1,1-difluoro-ethane, hydrogep sulphide, traces of C4 hydrocarbons and trace~ of am~onia.
In experiments 14, 15 and 18 the temperature was varied durin~
the in-situ fluoriding.
Table VI
Catalyst Composition of the catalyst base Composition of the base ma- material, pb~ per 100 pbw of the carrier pbw per 100 terial, carrier _ _ pbw of the cQrrier - nickel molybde- tunesten pho~pho-. num rus ________ ___---_____ ____________________ G 3.614.3 - 3.5 100 Al203 H 7.8 _ 25.5 ~ 24 SiO2- 76 Al203 I 3.0 - 9 5 - 75 sieve Y - 25 A1203 Table VII
Experiment No. 14 15 16 17 l8 19 Catalyst base materiAl, No. G G G H
: Liquid HG0* HG0* HG0* HG0*KER KER
Fluorine concentration in the liquid, ppmw 300 300 300 300 225 150 . Conditions during the in-situ fluoridin~
Average temp.C 212.5 239 235 235 130 175 Total pressure,bar 130 130 130 130 125 125 Space velocitY, kg l_l.h_l 1.01.0 1.0 1.0 2.0 2,0 :H2/liquid ratio, ~l.kg-1 1000 1000 1000 1000250 1000 Duration of the ex-periment, h 430 250 170 250 542 340 Average fluorine slip,%w 61.5 31.5 35 45 19 9 Temperature gradient,C 15 Fluorine content of the catalyst bed,~ Pbw of fluorine per 100 pb~
-o~ the carrier F1 3.96.1 4.0 4.831.5 11.8 F2 6.66.o 3.~ 4.326.5 5.6 ~6'7~
.
I o U~ ~~ 'I
O j ~l ~ o ,1 O ~ o o 1 "~
!g ' Ei o~
a I O t- ~ NO ~I
!o o,!
I o ~ ~1 ~ o I U~ ~ o U~ "
a I o 1 1 ~ lo ~ o 1, N
u~ ol U~
aE- 19 I o ~ o ~ 11 . I I C~J 'I
~ ~ o 11 E~
1 ~u oD O
,. I
!, ~ ', `" 1l ~ o o 1, O P~ P' h ~ ¦~
~ ~s a,1 o a~ b~ ~ h ~ r/ hO ~ ^ ~ h I
0 ~ bO rOd a ~ ~d ;4i ~d~} h a ,1 bn o 1 O ~) O r~ h P~ J~ ~ C) h ~h) h ~ ~h~ ~ ~h ~ h r~ h 1~
~j~ ~ h ~ ,~H ~d ~ 0 P~ ¦¦
8~30 Of the in-situ fluoriding experiments 14-19 stated in Tables VII and VIII, experiments 14_18 were carried out according to the invention.
Experiment 19 falls outside the scope of the present invention and has been included for comparison.
In experiments 14-18 an average slip above 10 %w was used. Furthermore, in experiments 14 such a gradient below 30C was used that the product of average slip and 6radient was smaller than 1000. In each of experiments 14-18 a uniform distribution of fluorine ~ver the catalyst bed was obtained, characterized by a quotient F2/F1 between 0.5 and 1.5.
In~experiment 19 an average ælip below 10 %w was used. In this experiment a non-uniform distribution of fluorine over the catalyst bed was obtained, characteri~ed by a quotient F2/F1 smaller than P.5.
'~
'
Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the fluoriding of a catalyst, in which process a fix-ed bed of catalyst particles is fluorided in-situ with the use of a constant or variable fluorine slip through the catalyst bed combined or not combined with a positive temperature gradient over the bed, provided that (a) the average fluorine slip (SA) amounts to at least 10 %w, (b) the temperature gradient (G) amounts to at most 30°C, (c) the product of SA (in %w) and G
(in °C) amounts to at most 1000, (d) a constant fluorine slip which on aver-age amounts to less than 40 %w is accompanied by a temperature gradient of at least 300/SA, and (e) a constant fluorine slip which on average amounts to at least 40 %w but less than 50 %w is accompanied by a temperature gradi-ent of at least 3/4 (50-SA).
(in °C) amounts to at most 1000, (d) a constant fluorine slip which on aver-age amounts to less than 40 %w is accompanied by a temperature gradient of at least 300/SA, and (e) a constant fluorine slip which on average amounts to at least 40 %w but less than 50 %w is accompanied by a temperature gradi-ent of at least 3/4 (50-SA).
2. A process as claimed in claim 1, in which process a constant fluor-ine slip which on average amounts to less than 40 %w is used in combination with a temperature gradient of at least 3/4 (50-SA).
3. A process as claimed in claim 1 in which process a temperature gradient is used which is less than 25°C.
4. A process as claimed in claim 3 in which process a temperature gradient is used which is less than 20°C.
5. A process as claimed in any one of claims 1-3, in which process an average fluorine slip of less than 50 %w is used in combination with such a temperature gradient that the product of slip and gradient is between 400 and 900.
6. A process as claimed in any one of claims 1-3, in which process an average fluorine slip of less than 50 %w is used in combination with such a temperature gradient that the product of slip and gradient is between 500 and 800.
7. A process as claimed in any one of claims 1-3, in which process an average fluorine slip of at least 50 %w is used in combination with such a temperature gradient that the product of slip and gradient is between 100 and 900.
8. A process as claimed in any one of claims 1-3, in which process an average fluorine slip of at least 50 %w is used in combination with such a temperature gradient that the product of slip and gradient is between 200 and 800.
9. A process as claimed in any one of claims 1-3, in which process the catalyst contains one or more metals having hydrogenative activity, supported on a carrier.
10. A process as claimed in any one of claims 1-3, in which process the catalyst contains one or more metals of Groups VIB, VIIB and VIII of the Periodic System, supported on a carrier.
11. A process as claimed in any one of claims 1-3, in which process the catalyst contains 0.05-5 parts by weight of one or more metals of Groups VIB, VIIB and VIII of the Periodic System supported on 100 parts by weight of carrier.
12. A process as claimed in any one of claims 1-3, in which process the catalyst contains 0.1-2 parts by weight of one or more metals of Groups VIB, VIIB and VIII of the Periodic System supported on 100 parts by weight of carrier.
13. A process as claimed in any one of claims 1-3, in which process the catalyst contains 0.05-5 parts by weight of one or more metals of Groups VIB, VIIB and VIII of the Periodic System supported on 100 parts by weight of carrier and in which 0.1-7.5 parts by weight of fluorine per 100 parts by weight of carrier are applied to the catalyst by in-situ fluoriding.
14. A process as claimed in any one of claims 1-3, in which process the catalyst contains 0.1-2 parts by weight of one or more metals of Groups VIB, VIIB and VIII of the Periodic System supported on 100 parts by weight of carrier and in which 0.5-5 parts by weight of fluorine per 100 parts by weight of carrier are applied to the catalyst by in-situ fluoriding.
15. A process as claimed in any one of claims 1-3, in which process the catalyst contains a metal selected from the metals of Groups VIB and VIIB of the Periodic System and, in addition, one or more metals from the iron group.
16. A process as claimed in any one of claims 1-3, in which process the catalyst contains molybdenum or tungsten or both molybdenum and tungsten and, in addition, nickel or cobalt or both nickel and cobalt.
17. A process as claimed in any one of claims 1-3, in which process the catalyst contains a metal selected from the metals of Groups VIB and VIIB of the Period System and, in addition, one or more metals from the iron group and in which 0.5-15 parts by weight of fluorine per 100 parts by weight of carrier are applied to the catalyst by in-situ fluoriding.
18. A process as claimed in any one of claims 1-3, in which process the catalyst contains a molybdenum or tungsten or both molybdenum and tungsten and, in addition, nickel or cobalt or both nickel and cobalt and in which 1-10 parts by weight of fluorine per 100 parts be weight of carrier are applied to the catalyst by in-situ fluoriding.
19. A process as claimed in any one of claims 1-3, in which process the in-situ fluoriding of the catalyst is effected by the addition of a suitable fluorine compound to a stream of liquid which is passed over the catalyst.
20. A process as claimed in any one of claims 1-3, in which process the in-situ fluoriding of the catalyst is effected by the addition of a suitable organic fluorine compound to a stream of liquid which is passed over the catalyst.
21. A process as claimed in any one of claims 1-3, in which process the in-situ fluoriding of the catalyst is effected by the addition of a suitable fluorine compound to a stream of liquid which is passed over the catalyst at a temperature of 100-400°C, a pressure of 5-200 bar, a space velocity of 0.5-5 litres of liquid per litre of catalyst per hour and a hydrogen liquid ratio of 200-2000 Nl/l.
22. A process as claimed in any one of claims 1-3, in which process the in-situ fluoriding of the catalyst is effected by continuously adding 20-2000 ppmw of fluorine in the form of a suitable fluorine compound to a stream of liquid which is passed over the catalyst.
23. A process as claimed in any one of claims 1-3, in which process the in-situ fluoriding of the catalyst is effected by the continuous addi-tion of 50-1000 ppmw of fluorine in the form of a suitable organic fluorine compound to a stream of liquid which is passed over the catalyst at a temperature of 100-400°C, a pressure of 5-200 bar, a space velocity of 0.5-5 litres of liquid per litre of catalyst per hour and a hydrogen/liquid ratio of 200-2000 Nl/l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NLAANVRAGE7504620,A NL180636C (en) | 1975-04-18 | 1975-04-18 | METHOD FOR FLUORIZING A CATALYST. |
| NL7514824A NL7514824A (en) | 1975-12-19 | 1975-12-19 | Insitu fluorination of catalyst beds - with control of fluorine proportion absorbed and temp. gradient (NL201076) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1067880A true CA1067880A (en) | 1979-12-11 |
Family
ID=26645113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA246,844A Expired CA1067880A (en) | 1975-04-18 | 1976-03-01 | Process for the fluoriding of a catalyst |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5953095B2 (en) |
| CA (1) | CA1067880A (en) |
| DE (1) | DE2616721A1 (en) |
| FR (1) | FR2307579A1 (en) |
| GB (1) | GB1545828A (en) |
| IT (1) | IT1059143B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2430263A1 (en) * | 1978-07-06 | 1980-02-01 | Shell France | PROCESS FOR "IN SITU" FLUORATION OF A CATALYST |
| DE3367786D1 (en) * | 1982-11-01 | 1987-01-08 | Shell Int Research | Process for the conversion of hydrocarbon oils |
| US5358628A (en) * | 1990-07-05 | 1994-10-25 | Mobil Oil Corporation | Production of high viscosity index lubricants |
| CN1045904C (en) * | 1992-10-28 | 1999-10-27 | 中国石化兰州炼油化工总厂 | In-situ fluorination process of catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1390359A (en) * | 1971-05-13 | 1975-04-09 | Shell Int Research | Process for the preparation of lubricating oil with high viscosity index |
-
1976
- 1976-03-01 CA CA246,844A patent/CA1067880A/en not_active Expired
- 1976-04-15 GB GB1544776A patent/GB1545828A/en not_active Expired
- 1976-04-15 IT IT2236876A patent/IT1059143B/en active
- 1976-04-15 DE DE19762616721 patent/DE2616721A1/en active Granted
- 1976-04-15 JP JP4193976A patent/JPS5953095B2/en not_active Expired
- 1976-04-15 FR FR7611199A patent/FR2307579A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2307579A1 (en) | 1976-11-12 |
| IT1059143B (en) | 1982-05-31 |
| JPS5953095B2 (en) | 1984-12-22 |
| DE2616721C2 (en) | 1987-07-02 |
| FR2307579B1 (en) | 1978-11-17 |
| JPS51126991A (en) | 1976-11-05 |
| GB1545828A (en) | 1979-05-16 |
| DE2616721A1 (en) | 1976-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2230760C (en) | Integrated lubricant upgrading process | |
| US4428862A (en) | Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons | |
| US4383913A (en) | Hydrocracking to produce lube oil base stocks | |
| US6231749B1 (en) | Production of high viscosity index lubricants | |
| WO1998006795A1 (en) | Hydrocarbon conversion process | |
| US4032474A (en) | Process for the fluoriding of a catalyst | |
| US4428825A (en) | Catalytic hydrodewaxing process with added ammonia in the production of lubricating oils | |
| EP0775184B2 (en) | Lubricating oil production with vi-selective catalyst | |
| US4695368A (en) | Process for producing high octane gasoline | |
| US5151172A (en) | Distillate hydrogenation | |
| EP0070125B1 (en) | Crystalline silica zeolite-containing catalyst and hydrocarbon hydroprocess utilizing the catalyst | |
| JP2007526381A (en) | Continuous production method of two or more base oil grades and middle distillates | |
| CA2157220C (en) | Desulfurization method for catalytically cracked gasoline | |
| US4089775A (en) | Low pour middle distillates from wide-cut petroleum fractions | |
| CA1067880A (en) | Process for the fluoriding of a catalyst | |
| KR101692547B1 (en) | Process for reducing haze in heavy base oil and hydroisomerization catalyst system having reduced haze | |
| US4997544A (en) | Hydroconversion process | |
| US3236765A (en) | Denitrogenation of hydrocarbon mixtures | |
| US3671423A (en) | Stabilizing hydrocracked lubricating oils | |
| US3896025A (en) | Production of improved lubricating oils | |
| US4600497A (en) | Process for treating waxy shale oils | |
| KR100997926B1 (en) | Process to prepare a base oil having a viscosity index of between 80 and 140 | |
| US4790927A (en) | Process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons | |
| Yan | Effect of metal on zeolite catalysts for extinction hydrocracking | |
| CN112601802A (en) | Haze-free heavy base oil at 0 ℃ and method for production |