Process to produce modified clay, modified clay produced and use thereof

Patent metadata

Field	Value
Publication number	US-10940460-B2
Application number	US-201615572675-A
Country	US
Kind code	B2
Filing date	May 9, 2016
Priority date	May 11, 2015
Publication date	Mar 9, 2021
Grant date	Mar 9, 2021

Abstract

An intercalated, modified and calcined smectite clay comprising (a) pillars comprising aluminum and: (i) at least one rare earth or lanthanide group metal; or (ii) at least one rare earth or lanthanide group metal and gallium; and (b) at least one ion-exchanged metal selected from the group consisting of aluminum, barium, beryllium, calcium, cerium, cesium, copper, chromium, gadolinium, gallium, germanium, hafnium, holmium, iron (II and III), lanthanum, lithium, magnesium, manganese, neodymium, potassium, praseodymium, rubidium, samarium, silver, selenium, sodium, strontium, tellurium, terbium, thallium, thorium, tin, titanium, uranium, ytterbium, yttrium, zinc and zirconium; wherein the clay is characterized by a basal d001 spacing equal to or greater than about 18.5 angstroms; and processes for making. The modified clays are suitably used as catalyst support-activators and when used in combination with metallocene catalyst precursor components, can provide active catalysts for polymerizing at least one olefin, preferably in the substantial absence of aluminoxanes or boron-containing compounds.

First claim

The invention claimed is:

1. An intercalated modified and calcined smectite clay comprising:
(a) pillars comprising aluminum and:
(i) at least one rare earth or lanthanide group metal; or
(ii) at least one rare earth or lanthanide group metal and gallium; and

(b) said clay comprising at least one ion-exchanged metal selected from the group consisting of magnesium, and zinc; and
wherein said clay is characterized by a basal d 001 spacing equal to or greater than about 18.5 angstroms and equal to or less than about 100 angstroms; and
wherein said clay activates a metallocene catalyst supported by said clay for olefin polymerization in the absence of aluminoxane or borate activators.

2. The clay composition of claim 1 wherein the pillars comprise at least one of cerium or lanthanum.

3. The clay composition of claim 1 comprising at least one deposited metal selected from the group consisting of catalytically active transition metals of Groups 3-10 of the Periodic Table and optionally at least one organoaluminum compound.

4. The clay composition of claim 1 wherein said clay is characterized by a basal d 001 spacing equal to or greater than 30 angstroms and equal to or less than 100 angstroms.

5. The clay composition of claim 3 comprising at least one organoaluminum compound.

6. A process for producing an intercalated modified and calcined smectite clay composition comprising steps:
(A) contacting an aqueous slurry comprising a smectite clay with an aqueous pillaring agent comprising at least one of aluminum, zirconium or chromium and: (i) at least one rare earth or lanthanide group metal; or (ii) at least one rare earth or lanthanide group metal and gallium; to form a solids-containing phase and an aqueous phase;
(B) separating the solids-containing phase from the aqueous phase formed in (A);
(C) contacting the separated solids obtained in (B) at least once with an aqueous Met m X n composition comprising at least one Met m X n compound, wherein Met m is at least one metal ion selected from the group consisting of magnesium, and zinc, and X n comprises at least one anionic species; and m and n=numerals that together satisfy the valence requirement for the combination of Met m and X n , to form a mixture comprising a solids-containing phase and an aqueous phase;
(D) separating the aqueous phase formed in (C) in order to form a new solids-containing phase;
(E) drying the separated, solids-containing phase from (D) in order to obtain dry solids and reducing said dry solids to a dry, particulate form; and
(F) calcining the dry, particulate from (E) to form a dry, pillared, solid olefin metallocene catalyst support-activator in particulate form.

7. The process of claim 6 , wherein X n comprises at least one anionic species independently selected from the group consisting of a halide selected from the group consisting of chloride, iodide, fluoride and bromide; bromate; chlorate; perchlorate; sulfate; sulfamate; carbonate; hydrogen-carbonate; carbamate; nitrite; nitrate; oxalate; phosphate; selenate; sulfamate; azide; alkoxide; amide, including NR 2 or R[CON(R)] a , wherein R is independently H or a C 1 -C 20 unsubstituted or substituted hydrocarbyl group and a=1-4; and carboxylate, including R[CO 2 ] b , wherein R is independently H or a C 1 -C 20 unsubstituted or substituted hydrocarbyl group and b=1-4.

8. The process of claim 6 wherein following separation of the solids-containing phase in (B), the solids-containing phase is extracted at least once with water.

9. The process of claim 8 wherein water extraction is repeated until upon separation from the solids, the separated water is free or substantially free of: (i) residual anions originally present in the aqueous pillaring agent; or (ii) unconsumed pillaring agent or byproduct thereof; or (iii) both (i) and (ii); wherein free or substantially free is confirmed by a conductance value of less than 20,000 μS/cm or a negative AgNO 3 test result, or both.

10. The process of claim 6 wherein contacting with Met m X n is carried out from 2 to about 10 times, and wherein Met m X n used in more than one contacting step is the same or different as Met m X n used in a prior contacting step, and including the separating step as in (D) between one or more contacting step.

11. The process of any one of claim 6 , wherein the pillaring agent is selected from the group consisting of a basic aluminum complex, a basic zirconium complex, a basic chromium complex and mixtures thereof.

12. The process of claim 6 , wherein calcining is conducted at a temperature in the range of about 110° C. to about 800° C. for about 1 hr. to about 10 hrs.

13. The process of claim 7 wherein Met m X n is selected from the group consisting of MgF 2 , MgCl 2 , Mg(OAc) 2 , Mg(NO 3 ) 2 , ZnCl 2 , ZnSO 4 , and mixtures thereof.

14. The process of claim 13 wherein Met m X n is MgCl 2 or ZnCl 2 or a mixture of MgCl 2 and ZnCl 2 .

15. A process for producing an intercalated modified and calcined smectite clay composition comprising steps:
(A) contacting an aqueous slurry comprising a smectite clay with an aqueous pillaring agent comprising aluminum and: (i) at least one rare earth or lanthanide group metal; or (ii) at least one rare earth or lanthanide group metal and gallium; to form a solids-containing phase and an aqueous phase;
(B) separating the solids-containing phase from the aqueous phase formed in (A) and repeatedly extracting the solids-containing phase with water and separating the water from the solids until the separated water is free or substantially free of: (i) residual anions originally present in the aqueous pillaring agent; or (ii) unconsumed pillaring agent or byproduct thereof; or (iii) both (i) and (ii); wherein free or substantially free is confirmed by a conductance value of less than 20,000 μS/cm or a negative AgNO 3 test result, or both;
(C) contacting the solids obtained in (B) at least once with an aqueous Met m X n composition comprising at least one Met m X n compound, wherein Met m is at least one metal ion selected from the group consisting of magnesium, and zinc, and X n comprises at least one anionic species; and m and n=numerals that together satisfy the valence requirement for the combination of Met m and X n , to form a mixture comprising a solids-containing phase and an aqueous phase;
(D) separating the aqueous phase formed in (C) in order to form a new solids-containing phase and contacting and mixing the new solids-containing phase with a new portion of aqueous Met m X n composition, wherein Met and X n are the same or different chemical species as selected in (C) and mixing and separating the resulting mixture comprising a solids-containing phase and an aqueous phase;
(E) optionally repeating step (D) at least one additional time, wherein following the last mixing and contacting with the Met m X n composition, water-washing by introducing distilled or de-ionized water to the separated solids-containing phase to form a solids-containing composition, mixing and separating the composition into a solids-containing phase and an aqueous phase;
(F) repeating the water-washing of step (E) until the separated aqueous phase is free or substantially free of X n ions in order to obtain a washed solids-containing phase, wherein free or substantially free is confirmed by a conductance value of less than 20,000 μS/cm or a negative AgNO 3 test result, or both;
(G) drying the washed solids-containing phase from (F) in order to obtain dry solids and reducing said dry solids to a dry, particulate form; and
(H) calcining the dry, particulate from (G)

Assignees

• Grace W R & Co

Inventors

• Jensen Michael D
• Mccauley John Robert
• Singleton Andrew G
• Michos Demetrius

Classifications

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• B01J21/16 Primary

  Clays or other mineral silicates · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F10/02 Primary

  Ethene · CPC title