GR65684B

Reduction and reoxidation of concentrate or self-reduced catalyst

Abstract

High melt flow olefin polymers suitable for such applications as injection molding, and the like requiring a narrow molecular weight distribution are produced using a catalyst made by reducing and reoxidizing a chromium catalyst on either a titaniumsilica cogel or a self-reduced silica-containing composition. In the first embodiment, a cogel formed by coprecipitating silica and titania, and containing a chromium compound, is treated in a non-oxidizing atmosphere, such as CO, hydrogen, N2 or a material decomposable to these materials, and thereafter reoxidized. In the second embodiment, a titanium-free chromium-containing catalyst is first heated in air or the like to dry the catalyst and oxidize the chromium after which it is heated in an inert atmosphere wherein the composition is self-reduced to give chromium in a lower valence state. The resulting selfreduced composition is then heated in a reducing ambient and then reoxidized as in the first embodiment.

GR65684B, drawing sheet 1 — Sheet 1 of 95

Term

Term ended

Expired 13 November 1993, 32.9 years ago.

2 claims: 2 independent, 0 dependent

1
57553 / 05-12-77 / US PHILLIPS PETROLEUM COMPANY BARTLESVILLE OKLAHOMA USA (43) Public Date Application Form :(72) Inventor (s): DEVI MAX P. MC DANIEL MELVIN B. WELCH (45) Publication Date DE : (74) Attorney:
2
30-03-1981 DEVI 03/81 YAZITZOGAOU EVANGELIA, Lawyer Piggy bank 2 106 74 ATHENS (54) Title SYMPTOM REHABILITATION AND REHABILITATION OR SELF-CATALOG (57) Summary Catalyst for the polymerization of olefins produced by reduction and re-oxidation of a chromium oxide catalyst either on a titanium silica gel or on a self-contained composition containing titanium-free silica. Pandanasis

Independent claims2

933 paragraphs in 55 sections, as filed

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SPECIAL MESSAGE -.

PHILLIPS PETROLEUM COMPANY, 'BARTLESVILLE Water Supply Company of the United States of America,' United States of America, '' j:. '' M.

SYNTHESIS REHABILITATION AND RENEWALS AND SELF-CATALOG

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r f, 'Polymrri? high-flow olefins, / suitable for applications /; i

SPSS'S '' - f. -'C = \ ·:? - ·; ; '<' Molding 0C * enchyveos and ta'paromoia, AT {opotai apaitodg / ,; <; 'vvyin distribution moriakonvaron, prepared by chrisimopoiiveos a catalyst?(Chloride-catalyzed chelated catalyst fiber over a titanium-vinyl plummeter with a "lead-in" vilica At first, incorporation of Sv bytes, a. formed from the vilica and titanium overlap and containing an inorganic / chromium, processed in an inorganic, CO, or atomic atom; ulcerated) /; ' /: i |;i '' .φ'i '.'-:' · '//' 'ι *, -1 simon these materials, and then they are oxidized. By the second: embodiment, is a chromium-free catalyst-titanium catalyst heated initially? inside / air / or similar medium to / drying of the catalyst and chromium oxidation and then heated within an inert atmosphere within which they are condensed to give low chromium;j., 0B;4..this-. The boiled potatoes are then heated in an ovenHoenvironment and then reoxidized as the first embodiment.

Supported chromium oxide catalysts are used in the preparation of polymeric olefins in a hydrocarbon solution to yield a product with excellent properties in many respects. These catalysts are also used in the preparation of polymeric olefins in a sludge system as the polymer is prepared in the form of small solid material particles suspended in a diluent. This method often referred to as a "particulate method" has the advantage of being more complex. However, certain control manipulations which are easily solved are often considered more difficult. For example, molecular weight can be carried out by Ag molarity with m, lower molecular weight (high molecular weight);l-m // -:- -.//

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It has a higher temperature. However, in the method of catheterization, there is a limited range of angiogenic agents in the bloodstream of any type of virus.; 'Flow of water' Expiry®nB ^^^n''2,11 By increasing the temperature, they would move the copolymer into the solution and thereby destroy this sludge or particulate method. r '' C :? ';'

Various techniques are known or employed to convert the catalyst to a polymeric barrier ;With a high melting index, these technically cause a loss in the distribution of molecular weights. * For example, U.S. Patent No. 4,041,224 describes the preparation of high-melting polymer polymers by impregnating titanium on a catalyst-containing catalyst containing chromium through the hot water inert or reducing dye and by subsequent reoxidation. * However, this or the technique is unpredictable with catalytic plugs free of charge - I do not consider the results of the method over the range of weight distribution patterns. 1 The object of the present invention is to provide a catalyst capable of delivering high melting rate polymers and a narrow molecular weight distribution and suitable for use with high performance, high performance polymer systems. : Molecular weights * A further object of the present invention is to provide a catalyst capable of delivering a suitable polymer in injection molding and other applications requiring high melting rate. : b ·:

According to the present invention, all. (i),. i

of a silica-titanium gel or a catalyst: a ... Millib. sr ·:. :

at the base of the villa, it goes down and then up

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There are two embodiments in the present invention. In the first case, two-stage silica gel titania subcutaneously | '-C ·' '* * »I ··'.! · <> ·: #> - 'i,. (· .. ...

on the other hand, on Monday a silica is brought in? in a first stage of oxidation and self-reduction (step 1) and then in a hygienic, hypertensive condition. (exil6.ioy<:2) which is immobilized to the stage of first embodiment, despite the fact that the environment is particularly conductive, environment of step 1: the first embodiment may use either a reducing or inert environment. Step 2 of the first embodiment and step 3 of the second embodiment are similar. These a (? two embodiments are discussed below in their schematic form

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Monday incorporation 1 2 silica exchangeExidant- - reductive - epoxy oxidation-Tir ------------ or co. -.: ./ 7: self reducing (inert). In a first embodiment of the present invention, the chromium-containing catalyst is a coexistant i.e. a catalyst produced by the precipitation of silica and a titanium-containing compound. The preparation of such coagulants is described under U.S. Patent No. 3,876,494. the content of which hereinafter co-operates by reference. Columns can be 77-J. ; 7 ·:

prepared e.g. by the addition of a mineral acid to the regular introduction of a porous elk4b.

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Containing the titanium acid compound to form a solid | 1 | | | ^^ | ^ or $; denotes: the earth without the solid 7 is 7x the largest; one hour, by / washing. of so-aged; 7Ϊ5 · 1µg>, 7-, '· M.-γ- · ·;? T7 ·. , U'M ^ - '· -:' ·> · - · Ύ; - ·: 7-.

Hydroxide to obtain a hydrocarbon-free alkaline metal by forming a mixture. In such a way, the rinsing was thoroughly washed, and at least normally removed. , of said organic kinetics and water, from said mixture to a solid form (dry) .7; * P) / mildew / contains chrome in quantity: generally printed. of traffic / road? 0.001 / to. 10% up. / 77.7 77gfeh? 7;'W /!7:7’:7i · -. "P / M;:·>7?:77777-W '<7.77., / - 77 - /: - 7. .

a type preferably of 0.1 to 6% and more preferably a type of 1% by weight of the coagulant i.e. the dry silica-titanium base. 'THE; chromium compound can be incorporated in a known manner. For example, a solution of hydrocarbons of a tert-butyl chromate may be used to impregnate the dry gel or an aqueous solution of a chromium oxide or trioxide chromate compound. drying or chromium type can co-precipitate with silica and titanium. * Hydrocarbon solutions of the p-linked organic chromium compounds such as the compounds of chromiodienene or bis-cyclopentadienylchromium (II) may also be used. You're the one. U.S. Patent Nos. 3,976,632, 3,349,007, and 3,709,863. Suitable chromium compounds are described herein.

The following is a detailed or first embodiment. The dry, silica-titanium coat preferably becomes fluidized and heated to an elevated temperature and comes in contact with a non-oxidizing environment with 10% oxidized in a 100% environment. The coat or the coat The coat is preferably a monoxide of <x | Do you own it? carbon and worth (Ng). Loudly

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- b -x | 2-109% Op, hai 98-0% N2. About these volumes are obtained with / β-100% -00% (volatile / gaseous solids / volumetric / volumetric);:, "Other non-oxidizing environment < an inert phallus such as carbon dioxide, carbon (COg), vacuum, the Sun and the reductive environment within 00 is H2 and at all times decompose to C0 and / or H2 such as hydrocarbons, alcohols, or ammonia and carboxylic acids. / i

Suitable hydrocarbons are anion, benzene, and the like materials are broken down into C and Hg.

Suitable alcohols for this mint are saturated or unsaturated at the time they are normally wet for convenience. "In!Fatty acids, particularly acetic acid, are preferred because of the high microcosm of their cohesiveness and availability. This is broken down by various mixtures of CO, CO,: C. xai HP. .-: ¾¾ blb 1 ® · x /> 7b '

The plug-in for this chromium unit; lightly lysed as a vick-plug, may contain from 0.1 to 20% other materials such as e.g. or alumina. The only limitation is that it does not contain titanium embedded. The titanium found in the plug is present in 0.1 to 10% by weight, preferably 0.5 to 5% by weight of the dry plug (gum).

* The cold shakes to heat up in a temperature that is processed in a non-oxidizing environment, in three ways. First, it can be brought to temperature in CO or in a hetero / reducing environment. Secondly, it can be brought to the appropriate temperature in the air and air is rapidly removed so as to avoid self-conduction within the usable inert environment to remove the ambient air afterwards. Catalytically, the catalyst may be | heat in a 'dormant' / 'H · / · ®®' / - '' / '

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B-IId material for transfer of material in a temperature-dependent manner. Lpt ·. · - .7 -.-./ - · τ - ·· ': · -' r · working after;the non-oxidizing environment, why avoiding it, nitrogen or other inert environments / is it blocking? of auto-regeneration.-..... It took a long time for her to say that she wasn jj jilt; h 'S': h | S'7 ~ 4?, J · Y + i? ' M7; '' - 'M./air') by pathway / iodine and then -hydrocyanide or hydration. Similarly, in the third method if the chromium is heated, does the reduction occur at different heating rates if used? Inert environments such as Nitrogen The processes are not necessarily harmful and are often preferred to show the following element (s). They're all four. are the processes within the spirit of the second embodiment rather than the first? The first embodiment with the use of obturator, the self-reduction step can be omitted and yet an excellent product can be achieved. s • During the second embodiment, the catalyst is either silica-free-titanium silica or co-precipitation. As is well known in the art, the base may contain 0.1 to 20% other materials.

I: The first stage of oxidation and self-reduction is referred to as a single step, although in reality it comprises two subpopulations in that the initial oxidation can occur when the catalyst has been out of time for the first time. As such a catalyst has been oxidized during the final stage of its initial treatment, can it undergo the self-reduction step without any further processing or can it be processed? high-temperature air for drying and oxidation: this immediately before self-reduction. It is also possible to use as a starting material a silica-based base / chromium compound in trivalent form.;The earth will be given and it is in self-reduction.

The environment during the auto-regeneration step

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iv || i, /, is / tfisi..this extraterrestrial non-oxidant / environment, zz Z / p. ft ';' -zv-f / '', of step 1i of the first embodiment. The preferred material is1 az otoVf other ^ dogan1 epileptically emptied the vacuum Z / o / sun (: H, · i)

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G 4 "Wji n -acidic conductive / processed conductive" stage 1 "of the first / first embodiment. The preferred material is CO 2: CO mixturesL.® P1 it was written by reference to the first incubation. However, hydrogen and other non-degradable materials may be used in a reductive dye described above in the first inoculant reducing dyes.

As to the third stage, or epanoxidosis, it is performed in a substantially or "gravely non-toxic" manner to the epanoxidosis (step 2) of the first injectable and preferably ambient air. Both of the inorganic compounds can be used to further oxidize the environment as NgO nitrogen peroxide, NOg nitrogen dioxide, NO nitrogen monoxide, hydrogen oxide or Cl-containing halide compounds. .

Ή The temperature for the first reduction period:will be at least 600 ° C and generally within the range of 6501100 ° C, preferably 700-925 ° C. temperatures 760-925 ° C are particularly suitable for CO and mixtures of CO + Ng; 01 times for this

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Epoxy oxidation temperatures are from 400-1000 ° C, preferably 500-925 °. C, and more preferably / 6; 90-800 ° C. The time for epoxidobacterial step is at least 10 minutes, preferably ΐ / 2-10; and most preferably 1 / up to 4 hours. Of course ol times at heatwave ΐ can have an ozone-depleting environment which has greatly reduced the ozone / / z / z // '// fstefeziZ; / -Z: - ζ ζ, ZZZZZipii '··. ·· - · ''; ; ;.:. ZZ'Z · / ·

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was taken care of, (the '' Offville ''; is it? at the final, stage of its formation?) and is now almost like (see 'in the second part of the chapter' /!) of the Auto-Reduction. you are lively, live less- static / valentine, generally will be trivalent as soon as they are airborne, at least long enough. 4 part of chromium; 7p; 7p; ; >. · - ·, ·; ''; .1 lr~ O '·'. \, ® 7 /, - -. ·. ··. -, ·. ' · ·. '·· -, ·. · Contain: in the form of chromium trioxide (CrO). All1 A / '.! A / L-A. A "maxa,!". i · A> · µ · -; · · γA 'A; ·1 - Ag) A'a7 · '; - A -> A- Alcohol (t03; simply added elt (the base to provide material already in the appropriate form for self-reduction in step 1. * 0), or heating temperature will generally start at room temperature. In the time-to-thaw heats at temperatures of 650 ° C, a satisfactory oxide is obtained This heating step requires at least 6 minutes, preferably 30 minutes to 24 hours and most preferably from 2 to 7 hours. Alternatively or heating is switched off. a silk temperature of 250 ° to 1000 ° C, and the material is maintained at that temperature in an oxygen-containing environment for a time as described above. As for epoxy oxidation, a usable medium containing 10-100% oxygen and the remainder of this inert material to Ng. However, it seems to be environmentally friendly (after the temperature reaches a temperature below

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S® of the range 250-1000 ° C, preferably 650 ° C, stops the oxidation of the oxidizer and exerts an effect on it. : 1 A '' 'aa .....' lA '' 'lol. Even when the catalyst is formed?

CrOg, preferably in air reduction, is preferred to avoid or

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:. · '; . F · ip /. 'A'A' '' '- ·j’:'· I'- ·' - ', -.--- / 4 1 , touchscreen Chromium-after-humidity / atmospheric-atmosphere-atmosphere .., · / '' H; ·;? · Tl .- 'h'.1'' 4i · -. 4 '4', 4 \ '' * The self-induction step of step 1-integrator is executed:<i!The .600-lb. barrel-mounted camshaft.,;0, okay prefer? Ed5 | met | 17, ^ |) F925O pc.-;tor · L | , /Pi-6 £ePYa <s Keep warm at the time it is required to heat from the original temperature to the final temperature or temperature can be maintained at any value within said range. At 4: '4' '- H4Fiip ^' - any case of double heating time 'will be at least 5 minutes and will generally be within the range of FtCJv of minutes to 15 minutes preferably 20 minutes. at 10 o'clock, and with the highest being at least 3 o'clock X X no conductor 2 x 2 at this time and at such temperature

.. 1, above; without prejudice to step 1 of the first embodiment. Also note> c | -ΐ;;at stage 2 of the second? integration <6 environment '' '' A'fe ;. It is, however, changing from the inert environment to the second part of stage 1 to the reductive environment under used conditions, e.g. "00 | or the Reagent Thracians as above was unaffected. * Final epoxidation is performed at that time at the same temperature upstream of the first embodiment step 2 of the first embodiment. 1 j: C is carried out at a temperature of at least 100 C below the temperature used for the reduction step.

If desired, the catalyst of the present invention may be activated-a continuous activator. For example, the catalyst may be inserted through the top of a vertical one with compartments activated with the first gas used to process the catalyst introduced from the bottom of the first.

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of intermittent healing. 'Alternatively, vibrate to' 4 '!' il ·, r

, ........ ......... ,,, ......., using two or more compartments, with this gaseous process, if desired, for growth residence time. / 5 / jj / - / H. ·, ///. -.///22/1 // f / '/'

An exterior furnace may heat up each compartment at the desired temperature. ;While not used as a continuous actuator for the preparation of catalysts hereinafter described,> · / 77> 222; You have an elevated temperature. It is assumed that during incorporation or initial heating is performed in a non oxidizing atmosphere, no problems are encountered;coinciding with the introduction of the catalysts into the presence of air in the nipple :already heated

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The catalysts of the present invention may be used for the polymerization of at least one mono-1-olefin with 2 to 8 carbon atoms per molecule. * The invention has a particular application in the synthesis / homopolymers of ethylene and copolymers of ethylene mixtures of one or more comonomers having a 1-olefin moiety of 3 to 8 atoms. Examples of the co-only parts are at 1'-positively 1-propylene, 1-butene, 6-hexene, and the like, and conjugated or unsubstituted are 1-butyl, 3-butyl , 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-ezadienone and the like, and mixtures thereof. -The ethylene copolymers preferably consist of molar, at least.

90% to 90% preferably 95 to 99% polymerized /

Particularly preferred are ethylene, propylene lop ^ LtB ^ i; i; i; i; i V;

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The polymers are prepared to form 7 'of the inactivated and solubilized invention by polymerization.1 solutions,; polymorphism I, polymorphism appeared to be as a contractual armament and contact process. However, the catalysts of the invention invention are particularly!Suitable polymerizations for the production of high melting point (MI) polymers; polymers with a MI value of: 4 g / dl 4 mol / l 36, and upper modulus of modifiers;

Relatively small size to show commercial interest in applicators, or injection molding. The sludge method is generally carried out in an inert diluent or with paraffin - or in aromatic or cycloparaffinic hydrocarbons. For most ethylene polymers, a temperature of about 66-110 ° C is used. 'For example ; i, AAAAA; 'A'L, 7 A' *. · Ethylene homopolymers with a melting index of 5 to 36 being able to obtain it? contact with the catalyst of the present invention, while conventional catalysts, however conventionally activated, provide polymers with MI 8, especially 6 at its temperature two: 110 ° C reactor. Lower reactor temperature, both catalysts, i.e. the catalyst according to the present invention and conventional control (comparator) catalysts give shorter MI and higher ratios, HLMI / MI, so that comparisons are required.C.to run at that temperature. Highly polymers of HLMl / MI ratio of 33 to 38 and Mir / Mjj ratio of about 4 at 110 ° C reactor temperature. These are molded by injection molding through conventional devices.

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live differently / in different directions along the three curves. Oh, yeah, yeah ^^^ '^^' ^^T1 g «WellSquared at 0.4 triangles | o ~ Numbers represent temperature; air-catalyzed catalyst, any 'U i'h / i-catalyst having no other type of treatment / statement, just a single control. Are these catalysts coincidental? in the optimum / artisanal system by catalysts for the preparation of high-melting polymer / polymers. * The par-1 dotted box under the "? Infinite" squares (zi,?, Index ratio or; /.'/ · - '- ·'. ·· i /? /; /!;? / ·} '' 4- /: ·. '': Melting-temperature for polymers produced by the use of catalysts -consistent with the present invention> 4 ° C temperature numbers at which the temperature corresponds to the temperature at which they are or will be treated any air or epoxy oxidation, the temperature // '; /, -' / ;; / or used for epoxy after treatment with CO. Provided: the optimized temperature for the oxidation is not (or better) at the temperature for the CO treatment, the melting indices obtained are not as high as those at the curve. are higher than the catalyst control markers - and thus are shown to be treated within non-existent steam and subsequent effluent. They may be operated at this temperature. The temperature numbers on the cross-section for the third curve shown / given by the circles are brought to the CO treatment prior to stainless steel at 760 ° C. of the use of C0 treatment temperatures within the preferred range of 760-925 ° C and the in-air air oxidation temperatures within the preferred range; The elemental values were obtained by operation (test X)

The catalysts of the present invention may be%?amC.The : 4. : '444' '444'r..4: gW ^!

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desired, with conventional catalysts. 'Also if power is desired' '' · '= 11 = ,,: 17/7 ΐ |, ^ 4aT · „// - 71 '7. Hydrogen may be used to further increase the melt index ITI = M,; r; 7 '

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A series of silica-titanium coagulant catalysts containing 2% by weight of titanium in the form of titanium oxide and 1% chromium in the form of chromium acetate were prepared by coagulation.:Concentration (artificially aging, rinsing, impregnating with aqueous chromium acetate solution and drying by aisotropic / distillation with oxyethyl. The catalysts were activated; in galvanic tubes at 1 ° C using a heating rate of 3-5 ° .0 per minute and a gas flow of approximately 740 liters per hour. This gas flow corresponds to a surface linear velocity at 873.9 C of the order of 0.03 meters per second. i.,? '. ·· ..!? L »· · · '. '.- · «

30-80 ° C lysates were used during each active poetry and each catalyst was activated under a fluid bed condition. i.; ·. ,,·,.. , .... . , ./7/. .

Each activated catalyst was tested as to its ability; 4 / / / n / 7 / -, 1. , 3 ·. > -3-, · '· ...': 3-7--77 '' Vn; f 1 ' ? melting rate for ethylene polymerisation by particulate method in a 2 or 3 liter reactor of stainless steel with isobutane as a diluent at 500 PSKI to yield

5,000 grams of polymer per gram of catalyst. You are all '7 7 77-777 77' '3: 7' .. 7:-77/7 -7th instances or reactor temperature was 110 ° C. Melting point values determined according to ASTM i) 1238-621 state E (g / 10 min) were slightly adjusted to a productivity value of 5; polyethylene catalyst based grammar based on its correlations. MI and productivity. \ The HLMI value of the melting index at maximum load was determined by ASTM D 1238-65 ° C, F (g / 10 min). Determination of the distribution of molecular weights;

-3-.¾ 33 '3 *.;.;. : & · ''

r.ir '* dd' ./. . 7777 '' • 7 ': 77-- •' '77 // 7'7x $:? I77 / 7 '/?;i'iii'= 47- 7 =' ΐ !!

SI *

II!! Ϊ́ S:

what ·· hi.:· l ·?

I:

7i / 'j;> .i]L.p

-i-7 'i-wTSitr; ·

Z '! L |; n5p * 5 »4» f RX ·· »vpji £» ig ~ **'.,.t,

- IB -¾

~. ·

:. 747,, 7 3344 ~ 4444 s of hydrolyzate in the presence of quaternary IE, if any. i · '' 1 · »·« · 4 * 5 «! i * r * - .SIlirl-SiwSt.— 'B.- ·! -. . ·>! "* ·, ·." '"' *. ·· ... ....,. · .. -. . . "Ib, - ^, ..... - ^ n-. ,;

the molecules were - the same length, the weight of the m, the weight of the mw, the weight of the Mw species! f0t | XoivV with the1 average 11 H / H, v;;, ; ρ tMWj '! ·; , - '; ·' ·;· ''; 7 would be equal to 1. However, are there always some molecules? 1 =. Ί ij 7Xip7 '| 7 *; i ”^ f <W · ':' '=: γ · fA'C *' · '* \ 7' '/' 7:· 7 \ i /? ·> '' 7 ·P*: . | : '' -s * with min ft longer. Because the longest molecules exert a disproportionate effect on their polymer properties, does the average molecular weight based on the addition of the "molecular weights of all molecules / and having a non-zero, non-zero molecular weight? gave a true picture of the state in which the weight of the average molecular weight is used. * However, reason | M.</ M.the affects both polymer and polymer distribution with narrower distribution (smaller Mw/ M, / A smaller HLMI / MI ratio) .It is best to apply either extrusion at high velocity or injection molding. A (Conditions used and the results obtained are given in Table I to illustrate embodiment 1 of the invention.

M · / 7, 7 · = 77 ° C;T. : 77.7b /;' 7 » :· / 7 O 47 '> · /! · <?

• Y / m ·,

• = · 5. ',. · 7 '=? · /,, I ..

· '!. M,.,,, 7. ·ΊΊ '/7777 /7/77·ί?''ΜΜ;'''''

TABLE 1, 'Activation of a Catalyst in an Ozone-Free, Ozone-In-Air Environment';

A / A. Activation Method MI HLMI Time Output - Time.

(g / 10 min) MI you are min. g / g 'catalyst flask

<td> 1</td><td>Heating in the air 871® C for 5 hours</td><td> 5,2</td><td> 37,9</td><td> 58</td><td> 4970</td><td>A</td>

<td> 2</td><td>Heating in CO at 871 ° C for 3 hours, then into the air 871 ° C over 2 hours</td><td> 10,8</td><td> 35,8</td><td> 59</td><td> 5740</td><td>B.</td>

<td> 3</td><td>Heating in CO at 871 ° C (3 h then you are in the air 705 ° C over 2 hours</td><td> 20,7</td><td> 42,7</td><td> 80</td><td> 5150</td><td>B.</td>

<td> 4</td><td>heating in Ng at 871 ° C over 5 hours then you are in the air 600 ° C for 2 hours</td><td> 17,0</td><td> 37,5</td><td> 100</td><td> 4400</td><td>B.</td>

<td> 5</td><td>Heat in Ng at 871 ° C for 5 hours then you are in the air 705 ° C over 2 hours</td><td> 12,0</td><td> 37,5</td><td> 60</td><td> 5250</td><td>B.</td>

<td> 6</td><td>heating in Ng at 871 ° C for 6 h then in the air 760 ° C over 2 hours</td><td> 11,6</td><td> 37,9</td><td> 80</td><td> 5210</td><td>Bi</td>

<td> 7</td><td>heating within Ng at 871 ° C, 30 no --- in 3 hours you have 871®0, 70 Ng Ng for 2 h at 871 ° C, air at 650 ° C for 2 h</td><td> 6,3</td><td> 40,0</td><td> 84</td><td> 5830</td><td>B 2</td>

A - Conventional actuation test (B) in accordance with the present invention

Bi-Condensation impregnated with n-hexanol, in accordance with the invention.

B2 "Symbol impregnated with 30% TWEEN 20 (polyethylene (20) Sorbitan monolaurate). Product of ATLAS CHEMICAL INDUSTRIES according to the present invention. 71

I? f -I

The results show that the dynamic melting index of the unsubstituted chromium silane-titanium iodide in the present invention can be 1.2 to 4 times higher in a non-oxygenated environment such as e.g. in CO, Ng and vapors of certain organic compounds containing oxygen and then by oxidizing the product in air at or below that temperature. * From the MI of the produced polyethylene through the catalysts it appears that an initial heat treatment within CO is more effective than the other tested media. From the comparison of tests 2, 3 and 4 it is obvious that the initial heat treatment is carried out within 00 or Ng at 870 ° C or an oxidative oxidation treatment is preferably carried out at 870 ° C to further improve the MI of the catalysts. Works 6 and 7 show that both. Talents containing a smaller amount of oxygen-containing organic compounds, such as esters, nonionic surfactants, when heated within a non-oxidizing atmosphere and subsequently oxidized.

Example

A series of chromium acetate-containing silica-titanium co-catalysts was prepared, formed and dried as described by Example 1 and activated according to the previously described embodiments 1 and 2.

A second series of catalysts was prepared from a sample of silica containing 2% by weight of CrOg (chromium 1% by weight) on a dry base of the substrate in CrOg, formed by spraying a silica gel containing 0.1% of alumina. Basically unaltered catalyst can be malfunctioned with 952 degree commercial silica impregnation available

DAVISON CHEMICAL 00 with an aqueous solution Ci

ll p>

in air at about 129-204 ° C. In this and the following examples it will be referred to as Ti-free silica. Whole or free-Ti silica or used herein, and the following examples were prepared in the above manner in full of operations 13-15 by which or bypass is described hereinafter.

An experimental silica-oxide chromium catalyst was prepared in the manner described for the substrate in the absence of titanium. 'The preparation of such a porous silica is described in Art. 3,900,457 U.S. Pat. (19/8/75). It provides a high porosity silica which yields polymers with high melting point. The samples were activated according to the present invention.

Each of the activated catalysts was tested by ethylene polymerization as described in Example 1. All 1 melt index values were adjusted to a productivity level of 5000 grams of polyethylene per gram.

The conditions of catalyst activation and the results obtained are given in Table 2.

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<td>• Religion</td><td>V.</td><td> —“1</td><td></td><td></td><td></td><td></td>

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* CE - Conventional activation (1) - Not applicable (2) As used, or incorporation 2 may be used with catalysts with precipitated titanium or with silicon-free antitumor and (2) free catalysts - induction.

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In each series of catalysts, the catalysts of the invention according to embodiment 2 were compared to conventionally activated catalysts (assays or controls 1, 7, 13), and the catalysts of the invention were activated in accordance with embodiment 1. etc. The results indicate that ol oxide containing TGS chromium catalysts SUPPORT iizomenoi on silica or on a precipitated silica-titania and activated according to the present invention is improved as to the ability of the melt index of the resulting polymer to of identical catalyst but conventionally activated within TGS intake air. By comparing the operations of the invention 2 and 5 it is shown that the catalyst activated according to embodiment 2 additionally improves the ability of the melting index to embodiment 1 e.g. 14.7 MI for work No 2 to 19.2 MI for work No 5. The advantages of pre-oxidation and self-conduction of the catalyst prior to CO treatment etc. are clearly shown. that is followed by epoxidation, instead of omitting the stage of preliminary oxidation. * From the operations of the invention 3-6 shows a further contemplation of the present invention. That is, the duration of CO treatment affects the ability of the melting index. Thus, under these other conditions, the work catalyst No 3 gives a polymer with MI = 10 while the work catalyst No 6 gives a polymer with MI "22. Figures 11 and 12 show that with these other conditions or the pre-oxidation temperature used also affects the melting index of the polymers. For this particular catalyst, a pre-oxidation temperature of 649 ° C gives better results than a pre-oxidation temperature of 538 ° C.

1.»

: ‘1 &

Lee

Example 5 * A second set of catalysts activated unambiguously for embodiment 2 of the abatement can be prepared from the previously described coagulation.

Each of the catalysts was tested by ethylene polymerization as described in Example 1.

At the conditions of activation used and the results of the polymerization are shown in Table 3. The values of the melting index were adjusted to a productivity level of 5000 grams of polyethylene per gram of catalyst.

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Comments:

1. - Does not apply

2. by volume% methane / Ng

3. Saturated Ng with benzene vapor at about 23 ° C under atmospheric pressure.

4. Coal burning. Petrol / N 'air / Ng vapor and N.b endless parts of the upstream stage.

* From the inspection in Table 3 it is shown that the melting indices of the catalysts are improved by preliminary oxidation in air, rapidly by self-induction in the inert environment at the range of 600-1000 ° C and by their processing environment. This decomposition gives rise to reducing agents, and finally after the product is oxidized in air.

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· ··· p '\ -i *, ·:

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<3 3«

-.3 ^ H

That's right. 4. A series of catalysts actuated according to embodiment 2 of the present invention was prepared from the previously described catalytic coagulant.

Each catalyst was tested for ethylene copolymerisation with a small amount of a higher 1-olefin in one oz of stainless steel 2 liter reflux reactor under 550 PSIG ethylene in isobutane. At catalyst activation conditions and catalyst activation are used and the polymerization results are provided in Table 4. At work, they were selected to yield 5000 grams of polymer per gram of calcium. Melting index values were adjusted to a productivity level of 5000 grams of polymer per gram of catalyst.

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* o a? ja ja tx> <a. vp »« ω a cm the year

·;

-I Remarks »(l) - Not applicable

The results show that oh-crystals of the present invention are active in the ethylene / t-olefin copolymerization and that an excellent incorporation of the comonomer is achieved. The copolymers have a relatively narrow molecular weight distribution, characteristic of the catalysts of the invention.

'ΐ

S:

(Ώ * 3,

η •

Example 5. This example illustrates the effect of the self-conducting step on the silica-titanium gel and the free silicon-titanium silica. The coagulation had 2% titanium and 1% chromium and free titanium silica containing 1% chromium. From a comparison of Tasks 1 and 2 it is shown that the highest melting index was obtained by using a three-step process where self-conduction was selected prior to re-oxidation. * Project No. 7 shows that good results are obtained with a titanium-free substrate from a series of uses * air, nitrogen, CO before re-oxidation, Although work 5 and 6 show an improved melting index according to the invention where a titanium-free substrate is subjected to a reduction in pre-oxidation temperature if present a melting index equal to 1 without the use of the present invention.

The results are shown in Table 5.

Table 5. Effect of the preliminary oxidation step

Columns A and B having 2% T1 and 1% Cr., Reaction conditions were 110 ° C and 550 PSIG of ethylene in (sorbutane).

MI values were adjusted to 5000 gr / gr Activation do Air MI HLMI Time - Fri 3 hr 2 hr (g / lO Min) ~ One farm worker

Increase in heat gr / gr

No Catalyst> wattage (min) i IS • tr

S

L

Symptom A fC0 at 871 ° C. Compatibility A 'at 650 ° C N2 over 871 ° C Cluster B, N over $ 900 ° C Cluster B Air at 650 ° C N2 at 900OC

Free Silica Silicone Free Silica Silicone

Free Ng at 87 ° C

CO at 871 ° C Air 6509 ° C

3,J C ·

14,7 37,4 84 5130

19.9

13.9

16.9

3,4

3,3

4,8

4050

5270

5380

6240

5830

5230

* i

7 a. CO: 25% - Ng 75% r§) 4 * * 7 Reactor Temperature 109 ° C jf '/'! {• · M <·,

Example 6. Here is an aggregate example showing the advantage of embodiment 2. In this example an example of a silica-titanium coated with about 2% titanium, prepared according to Example 1 and containing 1% chromium reduction. The results are shown in Table 6 »

Table 6.Polymerizations of ethylene at 110 ° C in isobutane at 550 PSIG.

Opera- Aubis Heat Exchanger 'Activation' CO Treatment

CO / wg Time

CO% h ° C

Inside Heat- Air Time Weather Projects | mm 2 Working Hours ° C

Fm) kmin f) KEMITIS Ml MI gr / gr

(l) At MI values are corrected.

hl f':'ii. You ..

As shown, at work 2 and 4 at work 2 work at higher MI. However, the '' - '' - 7 also shows a higher MI than a conventional '' 4 '' or 'see' example 1 control task 1. w / o / w / w / w / w / w

/ !, W, aaaaaa or movement of air into the carbon monoxide because the percentage of CO is low enough that no combustion occurs.

rH 3 - 'f ·: 7 7

Example 7. This example shows the advantage of heating the free titanium silica in the second embodiment prior to the self-conducting temperature of the present air. In this example, a titanium-free silica containing chromium 135 was subjected to self-conduction either directly by heating at 871 ° C or by heating at an air temperature of 650 ° C or less. 871 ° C followed by carbon monoxide reduction for 3 h at 871 ° C followed by 2 h at 2 ° C at varying temperatures. The results are shown in Table 7.

Table 7.'Coat for 3 hours at 871 ° C.

Ethylene Polymers at 550 PSIG and Isobutane at 110 ° C Processing Saturn Intensive Air Generators, Oxygen Gr / gr

No. projects- Increase in heat - 2 hours without heat ° C min

- MI(1)

HLMI

MI (g / 10 min)

• iii; 31 ms;

.....

j 7

Ϊ ir fi

i / /

• ··' · ·:

Ϋ ·

Table g 7.- (Continued)

<td> 13</td><td>overcast 650 ° C,</td><td></td><td></td><td></td><td></td><td></td>

• J i y-1

Ml?

7 1 4

4th (1) MI has been corrected to a productivity of 5000 gp / gv.

It shows by comparison of 2 and 11, 3 and 12, 4 and 13, and 6 and 14, the best results are obtained from performing an initial in-air heating.

Example 8 "In this example, free titanium silica containing 1% chromium is used. * The temperature used during the auto-reduction step was changed. The results are shown in Table 8.

kU ii. t 7 • ->? -H 4 1 /

$ 7.

Table 8. In the process of the described treatment, the catalyst was treated with CO for 3 h at 871 ° C and re-oxidized at 704 ° C for 2 h. The polymerisations were selected in Isobutane at 110 ° C and 550 PSIG ethylene.

(i)

Gold Derivatives- Ml 'hull work (gr / 10 (min.) Gr / gr min)

HI, MI

MI

Air 650 ° C 90

Ng at 650 ° C at 1 l / 2 h CO at 871 ° C Air 650 ° C 60

N at 760 ° C

N at 760 ° C for 1 1/2 hoursL. at 871 ° C

Air at 650 ° C 81

N.The at 816 ° C for 2 hr at 871 ° C

Air at 650 ° C no

N 8710 c

Ng at 8710 C for 1 1/2 hours

5200

5040

5550

5000

2,3

2,9

4,8

5.3 (1); 0 MI corrected with productivity 5000 gr / gr.

if a

·£

As shown, as 650 ° C increases to 871 ° C or self-reducing temperature C increases, MI increases and lupus decreases.

HLMI. MI; 7 i:

'-. '7' · 'V «f. -l ·

Example 9. Titanium free silica was impregnated with titanium and subjected to reduction and reoxidization in accordance with the present invention. According to the invention there was a 1% chromium / all catalyst used to polymerize ethyl ether to fr / tjv,

170 ° C. The results are reported below:

Y7

'Work' Impregnated : Titanium 1,2% MI - 1,2 'Impregnated Titanium%

Impregnated titanium 6% MI - 65 Impregnated titanium 6% MI - 20 Boilers 1600 ° F for 2 hours, Eleven 1100 ° F for 2 hours

HLMI / MI = 83.

CO at 7000 ° C for 2 hours, air 450 ° C at 15 minutes (Low active, 2 hours 800 gr / gr)

HLMI / MI - 45

CO at 1600 ° F in 2 hours, air 1100 ° F in 2 hours (Low activity, 3 hours 1650 g / gr) HLMI / MI = 47 • ΐ /

The above example demonstrates that the Titanium-impregnated Substrates are polymerized with a widely distributed weight distribution (45-83 HLMI / MI at 107 ° C reactor temperature) which is essentially useless for either applications.

While the present invention has been described in detail for the sake of exploration, it is understood that the offense is not limited by the above examples and modifications are intertwined and may otherwise be carried out within the spirit and purpose of the present invention.

1: A method for activating a catalyst comprising a material (s) prepared from the slurry of a compound of titanium and silica to form a tapered, cementitious The catalyst comes in contact with a non-gaseous environment at a temperature of at least 600 ° C and a second stage according to said catalyst,>

• B.

'Ll

<td></td><td>drunk</td><td>one</td>

<td> / ·</td><td colspan="2">temperature</td>

<td>i. ' y <n</td><td>of</td><td rowspan="2">that about</td>

chromium to a lower valence state and wherein said non-oxidizing environment of said first step is a reducing agent under the conditions used loses said first step.

3, - A method according to claim 2 characterized in:

Said said catalyst is heated in air at a temperature within the range of 250-1000 ° C over a period of 20 minutes to 10 hours, after which said self-conducting step in nitrogen in hot water is then performed -925 ° C for at least 5 minutes, Said switchgear is executed in an environment comprising 2-100% carbon monoxide at 700-925 ° C over a period of time of 1/2 to 24 hours and said unauthorized in the range of 500-925 ° C for 1/2 to 10 hours.

4. - A method for the production of a catalyst based on free silicon-titanium and chromium-containing silicates, active on polymer olefins where at least part of said chromium is in the form of Cr03, characterized by the addition of said catalyst in an inert environment over time and temperature;

Said Cr03 in a state of lower saturation Satisfactory for self-conduction of at least

W: 'S i · ^ a 3 ·'

-fit after submitting the self-regenerating composition in a reducing environment at a temperature Possible to further reduce at least a portion of said chromium and thereafter eliminating the said compound within said temperature.

5. - A method according to claim 4, characterized in: Since said catalyst is subjected to said inert environment at a temperature within the range of 600-1100 ° C for at least minutes, and the resulting bands come into contact after said reducing environment at a temperature of 650-11 ° C. for at least 5 minutes, and so forth the composition comes in contact with an oxygen-containing environment without a temperature within the range of 450-1000 ° C.

6. - A method according to one of the preceding claims, characterized in that said inert environment is nitrogen, said reducing environment comprises 2-100% carbon monoxide and said oxygen-containing environment is 6 'air.

- A method according to one of claims 2 to 6, characterized in that said CrOg is obtained by incorporating said chromium into said base material initially CrOg.

8. - A method according to any one of claims 2 to 6, characterized in that said CrOg is obtained by heating said catalyst at the temperature set at 600-1100 ° C in the presence of air.

9. A method according to one of the preceding claims, characterized in that said chromium is present in an amount within the range of 0.1 to 5% by weight based on said weight of said material.

10. - In a catalyst according to one of the preceding, recent times.

11. - One method of polymerization at one or

I:

ii ii Si / 3 M 'i /' ·? 7 b

- 36 olefins are contacted by polymerization with a chromium-containing catalyst and a silica based catalyst, characterized in that the catalyst is used as claimed by claim 10.-

-o-o-o-o-o-o-o * In Athens on March 22, 1979

S. · xX fc-ip

·. '/ ¥. - v 'V.'·:

The Special Representative

humidity temperature humidity temperature humidity temperature humidity temperature 760 ° C air temperature activation temperature, not humidity <1 ° C

The Lawyer of Law

Contents55

73 members in 27 offices

This recordMember, by publication datePriority claim17 more offices are in the list below

Priority claims3

Priority claims
Document	Office	Kind	Date
85755377	United States of America	A	1977-12-05
857553	–	–	–
US19770857553	–	–	–

Members73

Family members, oldest first
Document	Office	Kind
US4151122A	United States of America	A	1979-04-24
DK496978A	Denmark	A	1979-06-06
FI783715A	Finland	A	1979-06-06
FI783715A7	Finland	A7	1979-06-06
NO784074L	Norway	L	1979-06-06
NO834446L	Norway	L	1979-06-06
AU4204478A	Australia	A	1979-07-05
JPS5486493A	Japan	A	1979-07-10
EP0002673A2	European Patent Office (EPO)	A2	1979-07-11
EP0002673A3	European Patent Office (EPO)	A3	1979-07-25
BR7807864A	Brazil	A	1979-07-31
BR7807864A	Brazil	A	1979-07-31
US4182815A	United States of America	A	1980-01-08
ES475691A1	Spain	A1	1980-01-16
GR65684BThis record	Greece	B	1980-10-18
CA1125734A	Canada	A	1982-06-15
CA1130778A	Canada	A	1982-08-31
ATA867978A	Austria	A	1982-09-15
YU282478A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1983-01-21
JPS584927B2	Japan	B2	1983-01-28
JPS5845207A	Japan	A	1983-03-16
AT370744B	Austria	B	1983-04-25
FI63763B	Finland	B	1983-04-29
PH16086A	Philippines	A	1983-06-20
FI63763C	Finland	C	1983-08-10
EP0002673B1	European Patent Office (EPO)	B1	1983-10-12
DE2862336D1	Germany	D1	1983-11-17
MX150888A	Mexico	A	1984-08-09
ATA44679A	Austria	A	1984-08-15
AT377411B	Austria	B	1985-03-25
SG24984G	Singapore	G	1985-08-16
ATA230082A	Austria	A	1985-12-15
YU40728B	Yugoslavia, later Serbia and Montenegro (until 2006)	B	1986-04-30
NO154428B	Norway	B	1986-06-09
AT380888B	Austria	B	1986-07-25
NO154428C	Norway	C	1986-09-17
NO155969B	Norway	B	1987-03-23
DK157287A	Denmark	A	1987-03-27
DK157287D0	Denmark	D0	1987-03-27
NO155969C	Norway	C	1987-07-01
JPS6322203B2	Japan	B2	1988-05-11
DK156958B	Denmark	B	1989-10-23
DK156958C	Denmark	C	1990-03-05
DK158231B	Denmark	B	1990-04-16
DK158231C	Denmark	C	1990-09-03
MX166057B	Mexico	B	1992-12-16
ZA989697B	South Africa	B	1999-04-29
CA2305551A1	Canada	A1	1999-05-14
WO9922684A1	World Intellectual Property Organization (WIPO)	A1	1999-05-14
AU9809198A	Australia	A	1999-05-24
PE126599A1	Peru	A1	2000-02-13
EP1027022A1	European Patent Office (EPO)	A1	2000-08-16
US6120783A	United States of America	A	2000-09-19
BR9814836A	Brazil	A	2000-10-03
CN1283094A	China	A	2001-02-07
KR20010031607A	Republic of Korea	A	2001-04-16
IL135455D0	Israel	D0	2001-05-20
AR017178A1	Argentina	A1	2001-08-22
CO5070626A1	Colombia	A1	2001-08-28
US6290979B1	United States of America	B1	2001-09-18
JP2001521994A	Japan	A	2001-11-13
EG22469A	Egypt	A	2003-02-26
TW539554B	Taiwan Province of China	B	2003-07-01
EP1027022B1	European Patent Office (EPO)	B1	2003-08-20
AT247445T	Austria	T	2003-09-15
ATE247445T1	Austria	T1	2003-09-15
DE69817388D1	Germany	D1	2003-09-25
ES2205564T3	Spain	T3	2004-05-01
CA2305551C	Canada	C	2004-05-25
DE69817388T2	Germany	T2	2004-06-24
KR100476911B1	Republic of Korea	B1	2005-03-17
CN1315446C	China	C	2007-05-16
JP4463419B2	Japan	B2	2010-05-19