WO2011084177A1 - Ocp catalyst with improved steam tolerance - Google Patents
Ocp catalyst with improved steam tolerance Download PDFInfo
- Publication number
- WO2011084177A1 WO2011084177A1 PCT/US2010/045299 US2010045299W WO2011084177A1 WO 2011084177 A1 WO2011084177 A1 WO 2011084177A1 US 2010045299 W US2010045299 W US 2010045299W WO 2011084177 A1 WO2011084177 A1 WO 2011084177A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- alkaline earth
- zeolite
- silica
- earth metal
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- 238000005336 cracking Methods 0.000 claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 238000010025 steaming Methods 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- -1 olefin hydrocarbons Chemical class 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 238000002352 steam pyrolysis Methods 0.000 description 1
- 238000004326 stimulated echo acquisition mode for imaging Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- 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
- C10G2400/20—C2-C4 olefins
-
- 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
- C10G2400/22—Higher olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to the cracking of olefins.
- this invention relates to improvements in catalyst for use in olefin cracking, where the catalyst has a high steam tolerance.
- Ethylene and propylene, light olefin hydrocarbons with two or three atoms per molecule, respectively, are important chemicals for use in the production of other useful materials, such as polyethylene and polypropylene.
- Polyethylene and polypropylene are two of the most common plastics found in use today and have a wide variety of uses for both as a material fabrication and as a material for packaging.
- Other uses for ethylene and propylene include the production of vinyl chloride, ethylene oxide, ethylbenzene and alcohol. Steam cracking or pyrolysis of hydrocarbons produces essentially all of the ethylene and propylene.
- hydrocarbons used as feedstock for light olefin production include natural gas, petroleum liquids, and carbonaceous materials including coal, recycled plastics or any organic material
- an important source is naphtha where larger paraffins and naphthenes are cracked to produce olefins.
- One means of producing ethylene and propylene is an olefin cracking process, where larger olefins in the C4 to C8 range are cracked to produce propylene and ethylene in high propylene to ethylene ratios.
- an olefin cracking process is integrated with a naphtha cracking unit, and the propylene is dramatically increased.
- the use of an olefin cracking unit can take lower value C4 to C6 byproducts to produce additional propylene and ethylene.
- the olefin cracking process uses a catalyst that deactivates during regeneration. This leads to replacement of the catalyst when regeneration no longer sufficiently reactivates the catalyst.
- the present invention is directed to an improved catalyst having a greater tolerance to steaming.
- the catalyst is a zeolite that is loaded with an alkaline earth metal after normal preparation.
- the zeolite is loaded with the alkaline earth metal to an amount between 0.1 wt% and 2 wt% of the total catalyst weight.
- a preferred alkaline earth metal is magnesium or calcium.
- Light olefins demand is growing.
- the primary production of light olefins is through cracking, either steam or catalytic cracking, and produces a product mix of ethylene and propylene. Adjustments in operating conditions, and the types of catalysts used can influence the relative amounts of propylene and ethylene produced. It is desirable to increase the light olefins yields because of the increased demand.
- One method of increasing yields is the addition of an olefins cracking process (OCP) for the production of light olefins from heavier, and less valuable, olefins.
- OCP olefins cracking process
- the olefin cracking process could be integrated with other refinery processes, such as a naphtha cracker for increasing the production of light olefins.
- Light olefins of commercial value are propylene and ethylene.
- the OCP process produces coke on the catalyst, and the catalyst needs to be periodically regenerated by burning off the coke.
- the OCP catalyst slowly deactivates during the regeneration due to the presence of hydrogen on the coke, which leads to formation of water vapor.
- the catalyst is susceptible to deactivation during the olefin cracking process. Deactivation can occur when oxygen- containing compounds are present in the feed.
- Oxygen containing compounds include alcohols, ethers, ketones, and other oxygenates that can be generated in upstream processes as by-products, or occur in the feedstream. Modifying the catalyst to have a high steam tolerance is therefore very important for a steady propylene production and plant operation. Improving the steam tolerance improves the life of the catalyst, and allows for more regeneration cycles.
- the active component of the OCP catalyst is Silicalite zeolite, treated by steam and acid-washed. Silicalite is in H-form and contains only traces of other charge balancing cations, such as Na + .
- the present invention found that modification of the OCP catalyst with magnesium improves catalyst steam tolerance.
- the present invention comprises treating an olefin cracking zeolite with an alkaline earth element, and then calcining the alkaline earth element loaded zeolite.
- an alkaline earth element For most catalysts in the petrochemical industry, the presence of alkali or alkaline earth elements is detrimental to the activity of the catalyst. However, in the instant invention, the loading of an alkaline earth element was found to substantially slow the loss of activity in an environment with steam.
- the alkaline earth elements are selected from one or more of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Preferred alkaline earth elements are magnesium and calcium.
- the alkaline earth elements are loaded onto the zeolite in an amount 0.1 wt.% and 2 wt.% of the total catalyst weight, with a preferred amount between 0.5 wt.% and 1 wt. %.
- a preferred zeolite is silicalite, with the silicalite having a silica to alumina ratio greater than 200, and a preferred ratio of silica to alumina greater than 400.
- the olefin cracking process subjects the catalyst to steam, which contributes to the deactivation of the catalyst.
- Experimental aging of the catalyst through exposure to steaming resulted in a loss of activity.
- the conventional OCP catalyst and a catalyst loaded with 0.6 wt% Mg were subjected to steaming conditions.
- the steaming conditions included a 2.3 vol.% H 2 0 in N 2 at 585°C.
- the activities, in arbitrary units, are compared.
- the data shows that the loading of the alkaline earth element substantially slows the rate of deactivation of the catalyst, such that the life of a catalyst modified with magnesium could be substantially extended.
- the catalyst can further include a binder.
- the binder is present in the catalyst is an amount between 10% and 75% by weight of the total catalyst weight.
- the binder is used to confer hardness and strength on the catalyst.
- binder materials include, but are not limited to, alumina, silica, aluminum phosphate, silica- alumina, zirconia, titania, and mixtures thereof.
- silica-alumina does not mean a physical mixture of silica and alumina but means an acidic and amorphous material that has been cogelled or coprecipitated.
- binders include other refractory oxides and clays such as montmorillonite, kaolin, palygorskite, smectite, attapulgite, kaolinite, saponite, and bentonite. While many binders are possible, a preferred binder is silica.
- the catalyst can be subject to further treatment, wherein the catalyst is subject to a finishing steaming treatment.
- the finishing steaming step is performed to improve the catalyst selectivity.
- the catalyst can be further treated to an acid. Acid washing of a catalyst can remove non- framework alumina to make for a more active catalyst.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst is present for use in an olefin cracking process. The catalyst is a zeolite that has been loaded with an alkaline earth metal. The alkaline earth metal loaded catalyst has an increased steaming tolerance and increases the useful life of the catalyst during the cracking process and the regeneration cycle.
Description
OCP CATALYST WITH IMPROVED STEAM TOLERANCE
FIELD OF THE INVENTION
[0001] This invention relates to the cracking of olefins. In particular, this invention relates to improvements in catalyst for use in olefin cracking, where the catalyst has a high steam tolerance.
BACKGROUND OF THE INVENTION
[0002] Ethylene and propylene, light olefin hydrocarbons with two or three atoms per molecule, respectively, are important chemicals for use in the production of other useful materials, such as polyethylene and polypropylene. Polyethylene and polypropylene are two of the most common plastics found in use today and have a wide variety of uses for both as a material fabrication and as a material for packaging. Other uses for ethylene and propylene include the production of vinyl chloride, ethylene oxide, ethylbenzene and alcohol. Steam cracking or pyrolysis of hydrocarbons produces essentially all of the ethylene and propylene. While hydrocarbons used as feedstock for light olefin production include natural gas, petroleum liquids, and carbonaceous materials including coal, recycled plastics or any organic material, an important source is naphtha where larger paraffins and naphthenes are cracked to produce olefins.
[0003] One means of producing ethylene and propylene is an olefin cracking process, where larger olefins in the C4 to C8 range are cracked to produce propylene and ethylene in high propylene to ethylene ratios. Typically, an olefin cracking process is integrated with a naphtha cracking unit, and the propylene is dramatically increased. The use of an olefin cracking unit can take lower value C4 to C6 byproducts to produce additional propylene and ethylene.
[0004] The olefin cracking process uses a catalyst that deactivates during regeneration. This leads to replacement of the catalyst when regeneration no longer sufficiently reactivates the catalyst.
SUMMARY OF THE INVENTION
[0005] The present invention is directed to an improved catalyst having a greater tolerance to steaming. The catalyst is a zeolite that is loaded with an alkaline earth metal after normal preparation. The zeolite is loaded with the alkaline earth metal to an amount between 0.1 wt% and 2 wt% of the total catalyst weight. A preferred alkaline earth metal is magnesium or calcium.
[0006] Other objects, advantages and applications of the present invention will become apparent to those skilled in the art from the following drawing and detailed description.
DETAILED DESCRIPTION OF THE INVENTION [0007] Light olefins demand is growing. The primary production of light olefins is through cracking, either steam or catalytic cracking, and produces a product mix of ethylene and propylene. Adjustments in operating conditions, and the types of catalysts used can influence the relative amounts of propylene and ethylene produced. It is desirable to increase the light olefins yields because of the increased demand. One method of increasing yields is the addition of an olefins cracking process (OCP) for the production of light olefins from heavier, and less valuable, olefins.
[0008] The olefin cracking process could be integrated with other refinery processes, such as a naphtha cracker for increasing the production of light olefins. Light olefins of commercial value are propylene and ethylene. The OCP process produces coke on the catalyst, and the catalyst needs to be periodically regenerated by burning off the coke. The OCP catalyst slowly deactivates during the regeneration due to the presence of hydrogen on the coke, which leads to formation of water vapor. In addition, the catalyst is susceptible to deactivation during the olefin cracking process. Deactivation can occur when oxygen- containing compounds are present in the feed. Oxygen containing compounds include alcohols, ethers, ketones, and other oxygenates that can be generated in upstream processes as by-products, or occur in the feedstream. Modifying the catalyst to have a high steam tolerance is therefore very important for a steady propylene production and plant operation. Improving the steam tolerance improves the life of the catalyst, and allows for more regeneration cycles.
[0009] Currently, the active component of the OCP catalyst is Silicalite zeolite, treated by steam and acid-washed. Silicalite is in H-form and contains only traces of other charge balancing cations, such as Na+. The present invention found that modification of the OCP catalyst with magnesium improves catalyst steam tolerance. The present invention comprises treating an olefin cracking zeolite with an alkaline earth element, and then calcining the alkaline earth element loaded zeolite. For most catalysts in the petrochemical industry, the presence of alkali or alkaline earth elements is detrimental to the activity of the catalyst. However, in the instant invention, the loading of an alkaline earth element was found to substantially slow the loss of activity in an environment with steam.
[0010] The alkaline earth elements are selected from one or more of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Preferred alkaline earth elements are magnesium and calcium. The alkaline earth elements are loaded onto the zeolite in an amount 0.1 wt.% and 2 wt.% of the total catalyst weight, with a preferred amount between 0.5 wt.% and 1 wt. %.
[0011] A preferred zeolite is silicalite, with the silicalite having a silica to alumina ratio greater than 200, and a preferred ratio of silica to alumina greater than 400.
[0012] The olefin cracking process subjects the catalyst to steam, which contributes to the deactivation of the catalyst. Experimental aging of the catalyst through exposure to steaming resulted in a loss of activity. The conventional OCP catalyst and a catalyst loaded with 0.6 wt% Mg were subjected to steaming conditions. The steaming conditions included a 2.3 vol.% H20 in N2 at 585°C. In the following table, the activities, in arbitrary units, are compared. The data shows that the loading of the alkaline earth element substantially slows the rate of deactivation of the catalyst, such that the life of a catalyst modified with magnesium could be substantially extended.
Table - Catalyst Activity
[0013] In one embodiment, the catalyst can further include a binder. The binder is present in the catalyst is an amount between 10% and 75% by weight of the total catalyst weight. The binder is used to confer hardness and strength on the catalyst. Examples of binder materials include, but are not limited to, alumina, silica, aluminum phosphate, silica- alumina, zirconia, titania, and mixtures thereof. In referring to the types of binders that may be used, it should be noted that the term silica-alumina does not mean a physical mixture of silica and alumina but means an acidic and amorphous material that has been cogelled or coprecipitated. In this respect, it is possible to form other cogelled or coprecipitated amorphous materials that will also be effective as binder materials. These include silica- magnesias, silica-zirconias, silica-thorias, silica-berylias, silica-titanias, silica-alumina- thorias, silica-alumina-zirconias, aluminophosphates, mixtures of these, and the like. Other binders include other refractory oxides and clays such as montmorillonite, kaolin, palygorskite, smectite, attapulgite, kaolinite, saponite, and bentonite. While many binders are possible, a preferred binder is silica.
[0014] Optionally, the catalyst can be subject to further treatment, wherein the catalyst is subject to a finishing steaming treatment. The finishing steaming step is performed to improve the catalyst selectivity. The catalyst can be further treated to an acid. Acid washing of a catalyst can remove non- framework alumina to make for a more active catalyst.
[OO 15] While the invention has been described with what are presently considered the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
Claims
1. A catalyst having a longer life for cracking olefins comprising:
a zeolite that is loaded with an alkaline earth metal; and
the zeolite is calcined.
2. The catalyst of claim 1 wherein the zeolite is a silicalite.
3. The catalyst of claim 2 wherein the zeolite has a silica to alumina ratio of greater than 200.
4. The catalyst of claim 3 wherein the zeolite has a silica to alumina ratio of greater than 400.
5. The catalyst of claim 1 wherein the alkaline earth metal is selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or mixtures thereof.
6. The catalyst of claim 5 wherein the alkaline earth metal is selected from the group consisting of magnesium, calcium and mixtures thereof.
7. The catalyst of claim 1 wherein the alkaline earth metal loading is between 0.1 wt% and 2 wt. % of the catalyst.
8. The catalyst of claim 7 wherein the alkaline earth metal loading is between 0.5 wt.% and 1 wt. %.
9. The catalyst of claim 1 further comprising a binder in an amount between 10% and 75% by weight of the total catalyst weight.
10. The catalyst of claim 9 wherein the binder comprises silica.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10842382.3A EP2512666A4 (en) | 2009-12-16 | 2010-08-12 | Ocp catalyst with improved steam tolerance |
CN2010800557392A CN102652038A (en) | 2009-12-16 | 2010-08-12 | OCP catalyst with improved steam tolerance |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/639,577 US8609567B2 (en) | 2009-12-16 | 2009-12-16 | OCP catalyst with improved steam tolerance |
US12/639,577 | 2009-12-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011084177A1 true WO2011084177A1 (en) | 2011-07-14 |
Family
ID=44143603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/045299 WO2011084177A1 (en) | 2009-12-16 | 2010-08-12 | Ocp catalyst with improved steam tolerance |
Country Status (4)
Country | Link |
---|---|
US (1) | US8609567B2 (en) |
EP (1) | EP2512666A4 (en) |
CN (1) | CN102652038A (en) |
WO (1) | WO2011084177A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6873133B2 (en) | 2015-11-24 | 2021-05-19 | ビーエーエスエフ コーポレーション | Flow catalytic cracking catalyst to increase butylene yield |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004020093A1 (en) * | 2002-08-29 | 2004-03-11 | Albemarle Netherlands B.V. | Catalyst for the production of light olefins |
US20060084568A1 (en) * | 2004-10-18 | 2006-04-20 | Filimonov Igor N | Hydrocarbon cracking catalyst using chemical liquid depositon and method for preparing the same |
WO2009092779A2 (en) * | 2008-01-25 | 2009-07-30 | Total Petrochemicals Research Feluy | Process for obtaining a catalyst composite |
US20090264693A1 (en) * | 2006-08-31 | 2009-10-22 | China Petroleum & Chemical Corporation | Process for the catalytic conversion of hydrocarbons |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4283306A (en) * | 1979-04-20 | 1981-08-11 | E. I. Du Pont De Nemours And Company | Crystalline silica and use in alkylation of aromatics |
CA1196617A (en) * | 1982-07-14 | 1985-11-12 | George E. Morris | Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas |
DE3370150D1 (en) | 1982-11-10 | 1987-04-16 | Montedipe Spa | Process for the conversion of linear butenes to propylene |
JPS5997523A (en) * | 1982-11-24 | 1984-06-05 | Agency Of Ind Science & Technol | Zeolite containing alkaline earth metal, its manufacture and manufacture of olefin |
AU565810B2 (en) * | 1983-08-15 | 1987-10-01 | Mobil Oil Corp. | Increasing catalytic activity of zeolites |
US4623636A (en) * | 1984-06-21 | 1986-11-18 | Union Oil Company Of California | Shock calcined crystalline silica catalysts |
US4721827A (en) * | 1985-02-20 | 1988-01-26 | Aristech Chemical Corportion | Crystalline magnesia-silica composites and process for producing same |
EP0229952A3 (en) * | 1985-12-30 | 1988-05-11 | Mobil Oil Corporation | A process for making light olefins from alcohols and ethers |
US5182012A (en) * | 1987-09-16 | 1993-01-26 | Chevron Research And Technology Company | Crystalline silicate catalyst and processes using the catalyst |
ES2122983T3 (en) | 1992-04-15 | 1999-01-01 | Evc Tech Ag | PRODUCTION OF VINYL CHLORIDE THROUGH CATALYTIC DEHYDROHALOGENATION. |
CN1157465C (en) * | 1999-11-17 | 2004-07-14 | 中国石油化工集团公司 | Catalytic cracking catalyst for preparing light oil with high yield and its preparing process |
FR2807750B1 (en) * | 2000-04-12 | 2002-06-07 | Inst Francais Du Petrole | SIMULTANEOUS SIMULATED MOBILE BED DISMUTATION AND SEPARATION PROCESS OF TOLUENE TO BENZENE AND XYLENES |
US7314963B2 (en) * | 2002-03-26 | 2008-01-01 | Uop Llc | Spherical catalysts to convert hydrocarbons to light olefins |
JP2005138000A (en) * | 2003-11-05 | 2005-06-02 | Jgc Corp | Catalyst, method for preparing catalyst and method for producing lower hydrocarbon using the same catalyst |
US7875755B2 (en) * | 2007-11-30 | 2011-01-25 | Uop Llc | Cracking C5+ paraffins to increase light olefin production |
EP2082801A1 (en) * | 2008-01-25 | 2009-07-29 | Total Petrochemicals Research Feluy | Process for obtaining modified molecular sieves |
US8137533B2 (en) * | 2008-10-24 | 2012-03-20 | Uop Llc | Mixture of catalysts for cracking naphtha to olefins |
EP2460784B1 (en) | 2009-07-30 | 2020-06-17 | Mitsubishi Chemical Corporation | Method for producing propylene and catalyst for producing propylene |
-
2009
- 2009-12-16 US US12/639,577 patent/US8609567B2/en active Active
-
2010
- 2010-08-12 CN CN2010800557392A patent/CN102652038A/en active Pending
- 2010-08-12 EP EP10842382.3A patent/EP2512666A4/en not_active Withdrawn
- 2010-08-12 WO PCT/US2010/045299 patent/WO2011084177A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004020093A1 (en) * | 2002-08-29 | 2004-03-11 | Albemarle Netherlands B.V. | Catalyst for the production of light olefins |
US20060084568A1 (en) * | 2004-10-18 | 2006-04-20 | Filimonov Igor N | Hydrocarbon cracking catalyst using chemical liquid depositon and method for preparing the same |
US20090264693A1 (en) * | 2006-08-31 | 2009-10-22 | China Petroleum & Chemical Corporation | Process for the catalytic conversion of hydrocarbons |
WO2009092779A2 (en) * | 2008-01-25 | 2009-07-30 | Total Petrochemicals Research Feluy | Process for obtaining a catalyst composite |
Also Published As
Publication number | Publication date |
---|---|
EP2512666A4 (en) | 2013-11-27 |
CN102652038A (en) | 2012-08-29 |
US8609567B2 (en) | 2013-12-17 |
US20110143919A1 (en) | 2011-06-16 |
EP2512666A1 (en) | 2012-10-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5828975B2 (en) | Catalyst regeneration | |
TWI402242B (en) | Process and catalyst for cracking of ethers and alcohols | |
US6417421B1 (en) | Hydrocarbon conversion catalyst composition and process therefor and therewith | |
AU2003225560B2 (en) | Catalyst compositions comprising molecular sieves, their preparation and use in conversion processes | |
US5866741A (en) | Transalkylation/hydrodealkylation of a C9 + aromatic compounds with a zeolite | |
US6074975A (en) | Hydrocarbon conversion catalyst composition and processes therefor and therewith | |
TWI651128B (en) | Catalyst and process for producing olefin | |
KR20120116469A (en) | Process for increasing a mole ratio of methyl to phenyl | |
US7880048B2 (en) | Process for producing propylene in the presence of a macroporous catalyst in the form of spherical beads | |
EP2991762B1 (en) | Catalytic methods for converting naphtha into olefins | |
JP4335144B2 (en) | Method for producing lower olefin | |
JP2023535309A (en) | Treatment of Paraffinic Naphtha with Modified USY Zeolite Dehydrogenation Catalyst | |
JP2011513198A (en) | Process for the production of light olefins from synthesis gas using a continuous two-stage reaction | |
CN108431177B (en) | Method for producing ethylene and propylene from naphtha | |
US8609567B2 (en) | OCP catalyst with improved steam tolerance | |
US20230357654A1 (en) | Process for converting naphtha to light olefins with separation | |
US6025293A (en) | Hydrocarbon conversion catalyst composition and processes therefor and therewith | |
JPWO2015152159A1 (en) | Process for producing unsaturated hydrocarbons | |
WO2015152160A1 (en) | Method for producing unsaturated hydrocarbon | |
RU2536472C2 (en) | Olefins cracking catalyst and method of its production | |
WO2019124519A1 (en) | Method for producing ethylene | |
RU2301108C1 (en) | Hydrocarbon dehydrogenation catalyst and a method for preparation thereof | |
US20230357107A1 (en) | Process for catalytically converting naphtha to light olefins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080055739.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10842382 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010842382 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |