US2003018230A1PendingUtilityA1

Metal containing small pore molecular sieve catalyst for oxygenates conversion

27
Priority: Jul 13, 2000Filed: Jul 30, 2002Published: Jan 23, 2003
Est. expiryJul 13, 2020(expired)· nominal 20-yr term from priority
Inventors:Zhongmin LiuLixin YangLei XuChenglin SunYi-Gang Xiong
Y10S423/30C07C 2529/83B01J 37/086Y02P30/20B01J 38/52Y02P20/584C10G 3/49Y02P30/40C07C 2529/85B01J 38/50C10G 2300/703B01J 29/85B01J 2229/18C10G 2300/4006C07C 1/20C10G 2400/20B01J 29/76C10G 3/45B01J 29/90C10G 2300/708
27
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Claims

Abstract

A molecular sieve and a molecular sieve catalyst containing a surface heat impregnated with a metal. The molecular sieve is heated in the presence of a metal containing solution at a temperature between 30° C. and 400° C. then separated from the metal containing solution. The molecular sieve and molecular sieve catalyst is used to make olefin from an oxygenate feedstock.

Claims

exact text as granted — not AI-modified
What is claimed is:  
     
         1 . A silicoaluminophosphate molecular sieve comprising a surface heat impregnated with a metal selected from the group consisting of Group IIA metals, Group IIIA metals, Group IB metals, Group IIB metals, Group IIIB metals, Group VIB metals, Group VB metals, Group VIB metals, Group VIIB metals, Group VIIIB metals, and mixtures thereof.  
     
     
         2 . The silicoaluminophosphate molecular sieve of  claim 1  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, the metal containing forms thereof, and mixtures thereof.  
     
     
         3 . The silicoaluminophosphate molecular sieve of  claim 2  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPQ-44, SAPO-47, and mixtures thereof.  
     
     
         4 . The silicoaluminophosphate molecular sieve of  claim 3  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-34A, SAPO-34B, and mixtures thereof.  
     
     
         5 . The silicoaluminophosphate molecular sieve of  claim 1  wherein the silicoaluminophosphate molecular sieve comprises 0.5 to 40 percent by weight of the metal.  
     
     
         6 . The silicoaluminophosphate molecular sieve of  claim 5  wherein the silicoaluminophosphate molecular sieve comprises 1 to 20 percent by weight of the metal.  
     
     
         7 . The silicoaluminophosphate molecular sieve of  claim 6  wherein the silicoaluminophosphate molecular sieve comprises 1 to 10 percent by weight of the metal.  
     
     
         8 . The silicoaluminophosphate molecular sieve of  claim 1  wherein the metal is selected from the group consisting of aluminum, magnesium, calcium, barium, lanthanum, titanium, chromium, iron, cobalt, nickel, copper, zinc, and mixtures thereof.  
     
     
         9 . The silicoaluminophosphate molecular sieve of  claim 8  wherein the metal is copper, zinc, or a mixture thereof.  
     
     
         10 . The silicoaluminophosphate molecular sieve of  claim 9  wherein the molecular sieve comprises the metal of 1 to 20 percent by weight based on the total weight of the molecular sieve.  
     
     
         11 . The silicoaluminophosphate molecular sieve of  claim 1  wherein the metal is a heat decomposition product of a metal acetate, metal nitrate, metal sulfate, or metal halide.  
     
     
         12 . The silicoaluminophosphate molecular sieve of  claim 1  wherein the surface is heat impregnated with the metal at a temperature from 30° C. to 400° C.  
     
     
         13 . The silicoaluminophosphate molecular sieve of  claim 12  wherein the surface is heat impregnated with the metal at a temperature from 120° C. to 260° C.  
     
     
         14 . The silicoaluminophosphate molecular sieve of  claim 13  wherein the surface is heat impregnated with the metal at a temperature from 160° C. to 220° C.  
     
     
         15 . A silicoaluminophosphate molecular sieve catalyst comprising: 
 a surface heat impregnated with a metal selected from the group consisting of Group IIA metals, Group IIIA metals, Group IB metals, Group IIB metals, Group IIIB metals, Group VIB metals, Group VB metals, Group VIB metals, Group VIIB metals, Group VIIIB metals, and mixtures thereof; and    a binder.    
     
     
         16 . The silicoaluminophosphate molecular sieve catalyst of  claim 15  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, the metal containing forms thereof, and mixtures thereof.  
     
     
         17 . The silicoaluminophosphate molecular sieve catalyst of  claim 16  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-47, and mixtures thereof.  
     
     
         18 . The silicoaluminophosphate molecular sieve catalyst of  claim 17  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-34A, SAPO-34B, and mixtures thereof.  
     
     
         19 . The silicoaluminophosphate molecular sieve catalyst of  claim 15  wherein the silicoaluminophosphate molecular sieve comprises 0.5 to 40 percent by weight of the metal.  
     
     
         20 . The silicoaluminophosphate molecular sieve catalyst of  claim 19  wherein the silicoaluminophosphate molecular sieve comprises 1 to 20 percent by weight of the metal.  
     
     
         21 . The silicoaluminophosphate molecular sieve catalyst of  claim 20  wherein the silicoaluminophosphate molecular sieve comprises 1 to 10 percent by weight of the metal.  
     
     
         22 . The silicoaluminophosphate molecular sieve catalyst of  claim 15  wherein the metal is selected from the group consisting of aluminum, magnesium, calcium, barium, lanthanum, titanium, chromium, iron, cobalt, nickel, copper, zinc, and mixtures thereof.  
     
     
         23 . The silicoaluminophosphate molecular sieve catalyst of  claim 22  wherein the metal is copper, zinc, or a mixture thereof.  
     
     
         24 . The silicoaluminophosphate molecular sieve catalyst of  claim 23  wherein the molecular sieve comprises the metal at 1 to 20 percent by weight based on the total weight of the molecular sieve.  
     
     
         25 . The silicoaluminophosphate molecular sieve catalyst of  claim 15  wherein the metal is a heat decomposition product of a metal acetate, metal nitrate, metal sulfate, or metal halide.  
     
     
         26 . The silicoaluminophosphate molecular sieve catalyst of  claim 15  wherein the surface is heat impregnated with the metal at a temperature from 30° C. to 400° C.  
     
     
         27 . The silicoaluminophosphate molecular sieve catalyst of  claim 26  wherein the surface is heat impregnated with the metal at a temperature from 120° C. to 260° C.  
     
     
         28 . The silicoaluminophosphate molecular sieve catalyst of  claim 27  wherein the surface is heat impregnated with the metal at a temperature from 160° C. to 220° C.  
     
     
         29 . The silicoaluminophosphate molecular sieve catalyst of  claim 15  wherein the binder is selected from the group consisting of alumina, aluminum chlorhydrol, clay, and mixtures thereof.  
     
     
         30 . A method of making a molecular sieve comprising: 
 a) mixing a metal containing solution with a silicoaluminophosphate molecular sieve, wherein the silicoaluminophosphate molecular sieve contains a template;    b) heating the mixture to a temperature between 30° C. and 400° C. to obtain a silicoaluminophosphate molecular sieve having a surface heat impregnated with a metal;    c) separating the heated silicoaluminophosphate molecular sieve from the heated metal containing solution; and    d) calcining the separated silicoaluminophosphate molecular sieve.    
     
     
         31 . The method of  claim 30  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, the metal containing forms thereof, and mixtures thereof.  
     
     
         32 . The method catalyst of  claim 31  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-47, and mixtures thereof.  
     
     
         33 . The method of  claim 32  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-34A, SAPO-34B, and mixtures thereof.  
     
     
         34 . The method of  claim 30  wherein the calcined silicoaluminophosphate molecular sieve comprises 0.5 to 40 percent by weight of the metal.  
     
     
         35 . The method of  claim 34  wherein the calcined silicoaluminophosphate molecular sieve comprises 1 to 20 percent by weight of the metal.  
     
     
         36 . The method of  claim 35  wherein the calcined silicoaluminophosphate molecular sieve comprises 1 to 10 percent by weight of the metal.  
     
     
         37 . The method of  claim 30  wherein the metal is selected from the group consisting of Group IIA metals, Group III metals, Group IB metals, Group IIB metals, Group IIIB metals, Group VIB metals, Group VB metals, Group VIB metals, Group VIIB metals, Group VIIIB metals, and mixtures thereof.  
     
     
         38 . The method of  claim 30  wherein the metal is selected from the group consisting of aluminum, magnesium, calcium, barium, lanthanum, titanium, chromium, iron, cobalt, nickel, copper, zinc, and mixtures thereof.  
     
     
         39 . The method of  claim 38  wherein the metal is copper, zinc, or a mixture thereof.  
     
     
         40 . The method of  claim 30  wherein the metal is a heat decomposition product of a metal acetate, metal nitrate, metal sulfate, or metal halide.  
     
     
         41 . The method of  claim 30  wherein the surface is heat impregnated with the metal at a temperature from 30° C. to 400° C.  
     
     
         42 . The method of  claim 41  wherein the surface is heat impregnated with the metal at a temperature from 120° C. to 260° C.  
     
     
         43 . The method of  claim 42  wherein the is surface heat impregnated with the metal at a temperature from 160° C. to 220° C.  
     
     
         44 . The method of  claim 30  wherein, the mixture is heated at autogeneous pressure.  
     
     
         45 . The method of  claim 30  wherein the metal containing solution has a metal concentration between 0.01 M and 1.0 M.  
     
     
         46 . The method of  claim 45  wherein the metal containing solution has a metal concentration between 0.05 M and 0.5 M.  
     
     
         47 . The method of  claim 46  wherein the metal containing solution has a metal concentration between 0.08 M and 0.3 M.  
     
     
         48 . The method of  claim 30  wherein the metal containing solution comprises metal salts selected from the group consisting of acetates, nitrates, sulfates, halides, and mixtures thereof.  
     
     
         49 . A method of making an olefin from an oxygenate feedstock comprising: 
 providing a catalyst comprising a silicoaluminophosphate molecular sieve having a surface heat impregnated with a metal selected from the group consisting of Group IIA metals, Group IIIA metals, Group IB metals, Group IIB metals, Group IIIB metals, Group VIB metals, Group VB metals, Group VIB metals, Group VIIB metals, Group VIIIB metals, mixtures thereof, and a binder; and    contacting the oxygenate feedstock with the catalyst.    
     
     
         50 . The method of  claim 49  wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-47, and mixtures thereof.  
     
     
         51 . The method of  claim 49  wherein the metal is copper, zinc, or a mixture thereof.  
     
     
         52 . The method of claim  51  wherein the silicoaluminophosphate molecular sieve comprises 1 to 20 percent by weight of the metal.  
     
     
         53 . The method of  claim 49  wherein the oxygenate feedstock comprises methanol.

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