Patent Application
20160074842
The present invention relates to a fluid catalytic cracking additive composition for cracking of heavy hydrocarbon feed stocks. In particular, the present invention relates to an additive composition comprising large crystallite low surface area alumina component in combination with phosphate compound in fluid catalytic cracking process and a process for preparing the same.
It is well accepted fact that the crude oils available to refineries are becoming heavier. Meanwhile, the demand for high value products such as gasoline and middle distillates is increasing. The trend towards heavy feedstock and urgent demand for high quality products coupled with tightening fuel regulations are presenting new challenges for refineries. Among the commercially available options, Fluid catalytic cracking (FCC) process is one of the key workhorses for conversion of heavy oils into high-value products.
Designing of FCC catalyst for processing heavy crudes is the key challenges to a catalyst developer for achieving these targets. The current generation FCC catalysts used today in cracking process for heavy oils are among the most sophisticated engineered catalysts, having high selectivity towards gasoline range products due to the presence of customized faujasite type zeolites having high acidity, higher hydrothermal stability and discrete pores in the range 6.5 Å to 13.5 Å. Heavy feeds contain high carbon residue, nitrogen, aromatics and contaminant metal such as nickel, vanadium, iron and copper. Processing such feeds while meeting changing product slate demand catalysts having higher metal tolerance, mesoporous active matrix and small pore zeolite. In a word, the catalyst activity, selectivity, particle size and shape, pore size and distribution, have to be optimized according to the properties of the heavy oils. Further, it is also very difficult to optimize all the said properties within FCC catalyst as this approach can adversely affect the performance of main catalyst. To overcome the above limitations use of additives as separate particles is in practice by the refiner to meet their specific objectives. There are several additive technologies available in the FCC technology market to obtain yields which meet refinery objectives.
Designing of such separate particle needs thorough understanding of interrelation between additive physico-chemical properties with activity/selectivity. The ability of the feed molecules to reach the active sites of the catalyst is important and for heavy resid molecules, mass transport limitations play an important role. In order to handle the challenges associated with cracking of resid molecules, it is essential to optimize the pore architecture and distribution of weak acid strength of additive formulations.
Cracking catalysts introduced from 1990's based on dispersible alumina and rare earth exchanged Y zeolites do possess improved hydrothermal stability and higher diesel selectivity (U.S. Pat. No. 6,528,447 & U.S. Pat. No. 6,114,267). However, as the zeolitic material is part of catalyst microsphere and as the main cracking acid sites present in zeolites are concealed under the coke, effect of matrix cannot be fully exploited in the formulations referred earlier.
WO 97/12011 relates to a process and product for bottom cracking, comprising of aluminosilicate, wherein a SiO2 component is chemically compounded with an alumina component, an acid dispersible alumina, clay and non-dispersible alumina. In this composition, alumino-silicate is prepared by mixing in an aqueous medium, a C2 to C20 alkoxides hydrolysed with water. Additive besides containing vanadium trap also contain phosphate containing compound. Use of high concentration (>25 wt %) boehmite alumina in combination with large pore alumina for cracking of heavy hydrocarbon molecules is not disclosed here.
U.S. Pat. No. 4,576,709 refers to upgrading of residual oils to gasoline product with a coke selective and metal stable faujasite crystalline zeolite catalyst comprising at least 40 weight percent of alumina and rare earth metals. This patent does not disclose use of boehmite alumina and large pore alumina. U.S. Pat. No. 4,692,236 deals with catalytic cracking process for heavy oil which comprises contacting heavy oil with a particulate mixture of a crystalline aluminosilicate-containing cracking catalyst particle and an alumina particle and/or a phosphorus-containing alumina particle mixed in the weight ratio of 80/20-20/80, under cracking conditions. Use of phosphate treated boehmite alumina for creation of weak acid sites and large pore alumina for easy diffusion of the heavy hydrocarbon molecules is not disclosed here.
Thus the object of present process is to offer a catalytic solution for up-gradation of heavier hydrocarbons mainly containing concarbon from 1-5 wt %, metals from 5-120 ppm as an additive. Another object of present invention is to crack heavier hydrocarbons mainly to diesel range products (LCO and naphtha). Yet another object of this process is to reduce the coke.
Accordingly, the present invention provides a catalytic cracking additive composition comprising:
Wherein the catalytic cracking additive having ABD in the range of 0.80-0.90 gm/cm3, attrition index <5 and average pore diameter of 100 Å to 200 Å.
In an embodiment of the present invention, the boehmite alumina has surface area in the range of 20-60 m2/gm and crystallite size greater than 500 Å.
In another embodiment of the present invention, the dispersible alumina is selected from pseudo boehmite, Catapal B, Pural 200, Disperal 40 and Pural 400.
In another embodiment of the present invention, the colloidal silica is selected from sodium or ammonium stabilized or silica acid, having residual soda lower than 0.3 wt %, ammonia lower than 0.3 wt %, silica content ranging from 20-45 wt % and particle size from 10-400 nm.
In another embodiment of the present invention, the clay has particle size in the range of 1 to 5 micron.
In yet another embodiment of the present invention, the phosphorous containing compound is selected from the group consisting of phosphoric acid, di-ammonium hydrogen phosphate (DAHP) and mono-ammonium hydrogen phosphate.
In an embodiment of the present invention, the invention provides a process for preparing the catalytic cracking additive comprising of:
In yet another embodiment of the present invention, the calcination in step (a) is performed at a temperature of 500° C. to 600° C. for a period of 1-3 hr.
In an embodiment of the present invention, stifling in step (b) is performed for a time period of 2-3 hrs.
In an embodiment of the present invention, stifling and milling in step (c) is performed for a time period of 2-3 hrs.
In an embodiment of the present invention, the boehmite alumina obtained in step (a) has the crystallite size over 500 Å.
In an embodiment of the present invention, the phosphate source in step (b) and step (d) is selected from the group consisting of phosphoric acid, di-ammonium hydrogen phosphate (DAHP) and mono-ammonium hydrogen phosphate.
In an embodiment of the present invention, the acid in step (c) is selected from nitric acid, formic acid and acetic acid.
In an embodiment of the present invention, the alumina used in step (c) is having average pore diameter from 30-400 Å.
In an embodiment of the present invention, silica in step (e) is selected from sodium or ammonium stabilized or silicic acid, having residual soda lower than 0.3 wt %, ammonia lower than 0.3 wt %, silica content ranging from 20-45 wt % and particle size from 10-400 nm.
In an embodiment of the present invention, the invention provides a process for reducing coke yield and bottom yield comprising contacting a hydrocarbon feed with a catalyst and the fluid catalytic cracking additive composition as claimed in claim 1, wherein the bottom yield is reduced by 0.5-2 wt % and coke yields by 1-2 wt %.
In an embodiment of the present invention, the additive is in the concentration of 5-25 wt % with respect to the catalyst.
In an embodiment of the present invention, the hydrocarbon feed has concarbon in the range of 1-5 wt % and metals from 5-120 ppm.
In an embodiment of the present invention, the Total Cycle Oil (cut point 150° C. to 370° C.) is over 34 wt %.
The present invention discloses an additive composition for cracking of heavy hydrocarbon feed stocks. The present invention also discloses a process for preparing the said additive composition.
Cracking of heavy hydrocarbon petroleum feed stocks involves parameters such as weak acid sites, which are distributed on large pore mesoporous materials. The present invention addresses these parameters. Synergy between large pore alumina with customized low surface area and high crystallite size boehmite alumina from aluminum trihydrate as raw material leads to enhanced performance of the catalyst of present invention when compared to prior art catalyst additives. The boehmite alumina is the main creator of weak acid site when coupled with phosphate source. This enhances the uniform distribution of weak acid sites in the large pore alumina matrix, which in turn enhances the overall activity of catalyst performance to crack heavy hydrocarbons molecules to value added products.
In an embodiment of the present invention a catalytic cracking additive composition is disclosed, comprising boehmite alumina, dispersible alumina, colloidal silica, clay and a phosphorous containing compound. In another embodiment the catalyst has ABD in the range of 0.80-0.90 gm/cm3, attrition index <5 and average pore diameter of 100 Å to 200 Å.
In accordance with the present invention the boehmite alumina is present in the range of 30-50 wt % and has surface area in the range of 20-60 m2/gm and crystallite size greater than 500 Å. In accordance with the present invention the dispersible alumina is present in the range of 5-30 wt % and is selected from pseudoboehmite, gamma-alumina, and alpha-alumina, Catapal B, Pural 200, Disperal 40 and Pural 400.
In accordance with the present invention the colloidal silica is present in the range of 5-25 wt % and is selected from sodium or ammonium stabilized or silica acid, having residual soda lower than 0.3 wt %, ammonia lower than 0.3 wt %, silica content ranging from 20-45 wt % and particle size from 10-400 nm. In accordance with the present invention, clay is present in the range of 10-50 wt % and has particle size in the range of 1 to 5 micron.
In accordance with the present invention the phosphorous containing compound is present in the range of 5-15 wt % and selected from the group consisting of phosphoric acid, di-ammonium hydrogen phosphate (DAHP) and mono-ammonium hydrogen phosphate.
Another aspect of the present invention also discloses the process for preparing the catalytic cracking additive composition, wherein the process comprises steps of:
In accordance with the present invention, the calcination of alumina trihydrate is performed at a temperature of 500° C. to 600° C. for a period of 1 hr. The stifling of water containing phosphated boehmite alumina is performed for a time period of 2-3 hrs. In accordance with the present invention, the stifling and milling performed to obtain alumina gel is in the range of 2-3 hrs.
In an embodiment of the present invention, the stifling of water containing phosphated boehmite alumina is performed for a time period of 2-3 hrs and, the stifling and milling performed to obtain alumina gel is for a time period of 2-3 hrs. In an embodiment, the boehmite alumina obtained in step (a) has the crystallite size over 500 Å.
In accordance with the present invention the dispersible alumina is present in the range of 5-30 wt % and is selected from pseudoboehmite, Catapal B, Pural 200, Disperal 40 and Pural 400 and can be partly substituted with gamma-alumina, and alpha-alumina.
In accordance with the present invention the colloidal silica is present in the range of 5-25 wt % and is selected from sodium or ammonium stabilized or silicic acid, having residual soda lower than 0.3 wt %, ammonia lower than 0.3 wt %, silica content ranging from 20-45 wt % and particle size from 10-400 nm. In accordance with the present invention, clay is present in the range of 10-50 wt % and has particle size in the range of 1 to 5 micron. In accordance with the present invention the acid in step (c) is selected from nitric acid, formic acid and acetic acid. In accordance with the present invention the alumina used in step (c) is having average pore diameter from 30-400 Å.
In accordance with the present invention the phosphorous containing compound is present in the range of 5-15 wt % and selected from the group consisting of phosphoric acid, di-ammonium hydrogen phosphate (DAHP) and mono-ammonium hydrogen phosphate.
In yet another aspect of the present invention, a process for reducing coke yield and bottom yield is disclosed, said process comprising contacting a hydrocarbon feed with a catalyst and catalytic cracking additive. In an embodiment, when the process is carried out employing the said additive, the bottom yield is reduced by 0.5-2 wt % and coke yields by 1-2 wt %. In accordance with the present invention the additive is in the concentration of 5-25 wt % with respect to the catalyst.
In an embodiment the hydrocarbon feed has concarbon in the range of 1-5 wt % and metals from 5-120 ppm. In yet another embodiment, the total cycle oil (TCO) (cut point 150° C. to 370° C.) is over 34 wt %.
Having described the basic aspects of the present invention, the following non-limiting examples illustrate specific embodiment thereof.
The details examples for the said additives are given below where the catalyst prepared under Example-1 is without boehmite alumina and catalyst additive prepared under examples 2, 3, 4 and 5 are the catalyst prepared under novel composition and process technique discloses in the present invention.
1.1 Preparation of alumina gel: 324.68 gm of Pural 400 grade alumina (LOI: 23 wt %) and 303.03 gm of PSB alumina (LOI=34) was dispersed in 1150 gm of DM water under stirring and milled for minimum 3 hrs. 25 gm of formic acid (85 wt %) was diluted with 100 gm of DM water and was added to alumina-DM water mixture under stifling. Mixture was kept for 20 minutes to form alumina gel.
1.2 Preparation of Clay Phosphate slurry: 411.76 gm of clay (LOI=15 wt %) was dispersed in 453 gm of DM water containing 5 gm of sodium-hexametaphosphate as dispersant. To this 121.36 gm of phosphoric acid (85 wt %) was added under stifling and aged for minimum 60 min to form clay-phosphate slurry.
1.3 Preparation of final catalyst precursor slurry: Alumina gel obtained under 1.1 was added to the clay-phosphate slurry obtained under step 1.2 followed by addition of 333.33 gm of ammonium polysilicate (LOI=70 wt %) under stirring to form final slurry.
1.4 Spray drying: Catalyst precursor slurry obtained under step 1.3 was spray dried in spray drier at inlet temperature 360° C., outlet temperature 125° C. and feed pressure of 2-4 kg/cm2.
1.5 The spray dried product obtained under step 1.4 was calcined in the furnace at a temperature of 550° C. for 1 hr to produce the final catalyst additive product.
2.1 Preparation of boehmite alumina: Alumina trihydrate was calcined at 550° C. for 1 hr to produce a chi-phase alumina. 200 gm of chi-phase alumina was re-slurried with 1140 gm of DM water and was kept in autoclave at 200° C. for 6 hrs. Bring down the autoclave temperature to room temperature and filtered the material. The wet cake obtained was then dried in oven for 6 hrs to form boehmite alumina.
2.2 Preparation of phosphated boehmite alumina: 303.03 gm of this boehmite alumina (LOI=34) prepared under step 2.1 was dispersed in 400 gm of DM water and 60.68 gm of phosphoric acid (85%) was added to it. The phosphated boehmite alumina slurry was then stirred for 2 hrs.
2.3 Preparation of alumina gel: 324.68 gm of Pural 400 grade alumina (LOI: 23 wt %) was dispersed in 750 gm of DM water under stirring and milled for minimum 3 hrs. 25 gm of formic acid (85 wt %) was diluted with 100 gm of DM water and was added to alumina-DM water mixture under stirring. Mixture was kept for 20 minutes to form alumina gel.
2.4 Preparation of Clay Phosphate slurry: 411.76 gm of clay (LOI=15 wt %) was dispersed in 453 gm of DM water containing 5 gm of sodium-hexameta phosphate as dispersant. To this 60.68 gm of phosphoric acid (85 wt %) under stirring was added and aged for minimum 60 min to form clay-phosphate slurry.
2.5 Preparation of final catalyst precursor slurry: Alumina gel obtained under 2.3 was added to the clay-phosphate slurry obtained under step 2.4, under vigorous stifling followed by addition of 333.33 gm of ammonium polysilicate (LOI=70 wt %) to form silica-alumina-clay-phosphate-slurry. Finally, phosphated boehmite alumina as prepared under 2.2 was added to this silica-alumina-clay-phosphate-slurry to form the final catalyst additive slurry.
2.6 Spray drying: Catalyst precursor slurry obtained under step 2.5 was spray dried with spray drier inlet temperature 360° C., out let temperature 125° C. and feed pressure of 2-4 kg/cm2.
2.7 The spray dried product obtained under step 2.6 was calcined in the furnace at a temperature of 550° C. for 1 hr to produce the final catalyst additive product.
3.1 Preparation of boehmite alumina: Initially alumina trihydrate was calcined at 550° C. for 1 hr to produce a chi-phase alumina. 300 gm of chi-phase alumina was re-slurried with 1710 gm of DM water and was kept in autoclave at 200° C. for 6 hrs. Bring down the autoclave temperature to room temperature and filtered the material. The wet cake obtained was then dried in oven for 6 hrs to form boehmite alumina.
3.2 Preparation of phosphated boehmite alumina: 454.55 gm of this boehmite alumina (LOI=34) prepared under step 3.2 was dispersed in 600 gm of DM water and 60.68 gm of phosphoric acid (85%) was added to it. The phosphated boehmite alumina slurry was then stirred for 2 hrs.
3.3 Preparation of alumina gel: 324.68 gm of Pural 400 grade alumina (LOI: 23 wt %) was dispersed in 750 gm of DM water under stirring and milled for minimum 3 hrs. 25 gm of formic acid (85 wt %) was diluted with 100 gm of DM water and was added to alumina-DM water mixture under stirring. Mixture was kept for 20 minutes to form alumina gel.
3.4 Preparation of Clay Phosphate slurry: 294.12 gm of clay (LOI=15 wt %) was dispersed in 324 gm of DM water containing 5 gm of sodium-hexameta phosphate as dispersant. To this 60.68 gm of phosphoric acid (85 wt %) under stirring was added and aged for minimum 60 min to form clay-phosphate slurry.
3.5 Preparation of final catalyst precursor slurry: Alumina gel obtained under 3.3 was added to the clay-phosphate slurry obtained under step 3.4, under vigorous stifling followed by addition of 333.33 gm of ammonium polysilicate (LOI=70 wt %) to form silica-alumina-clay-phosphate-slurry. Finally, phosphated boehmite alumina as prepared under 3.2 was added to this silica-alumina-clay-phosphate-slurry to form the final catalyst additive slurry.
3.6 Spray drying: Catalyst precursor slurry obtained under step 3.5 was spray dried with spray drier inlet temperature 360° C., out let temperature 125° C. and feed pressure of 2-4 kg/cm2.
3.7 The spray dried product obtained under step 3.6 was calcined in the furnace at a temperature of 550° C. for 1 hr to produce the final catalyst additive product.
4.1 Preparation of boehmite alumina: Initially alumina trihydrate was calcined at 550° C. for 1 hr to produce a chi-phase alumina. 350 gm of chi-phase alumina was re-slurred with 1995 gm of DM water and was kept in autoclave at 200° C. for 6 hrs. Bring down the autoclave temperature to room temperature and filtered the material. The wet cake obtained was then dried in oven for 6 hrs to form boehmite alumina.
4.2 Preparation of phosphated boehmite alumina: 530.30 gm of this boehmite alumina (LOI=34) prepared under step 4.1 was dispersed in 700 gm of DM water and 60.68 gm of phosphoric acid (85%) was added to it. The phosphated boehmite alumina slurry was then stirred for 2 hrs.
4.3 Preparation of alumina gel: 324.68 gm of Pural 400 grade alumina (LOI: 23 wt %) was dispersed in 750 gm of DM water under stirring and milled it for minimum 3 hrs. 25 gm of formic acid (85 wt %) was diluted with 100 gm of DM water and was added to alumina-DM water mixture under stifling. Mixture was kept for 20 minutes to form alumina gel.
4.4 Preparation of Clay Phosphate slurry: 235.29 gm of clay (LOI=15 wt %) was dispersed in 258 gm of DM water containing 5 gm of sodium-hexameta phosphate dispersant. To this 60.68 gm of phosphoric acid (85 wt %) under stirring was added and aged for minimum 60 min to form clay-phosphate slurry.
4.5 Preparation of final catalyst precursor slurry: Alumina gel obtained under 4.3 was added to the clay-phosphate slurry obtained under step 4.4, under vigorous stifling followed by addition of 333.33 gm of ammonium polysilicate (LOI=70 wt %) to form silica-alumina-clay-phosphate-slurry. Finally, phosphated boehmite alumina as prepared under 4.2 was added to this silica-alumina-clay-phosphate-slurry to form the final catalyst additive slurry.
4.6 Spray drying: Catalyst precursor slurry obtained under step 4.5 was spray dried with spray drier inlet temperature 360° C., out let temperature 125° C. and feed pressure of 2-4 kg/cm2.
4.7 The spray dried product obtained under step 4.6 was calcined in the furnace at a temperature of 550° C. for 1 hr to produce the final catalyst additive product.
5.1 Preparation of boehmite alumina: Initially alumina trihydrate was calcined at 550° C. for 1 hr to produce a chi-phase alumina. 400 gm of chi-phase alumina was re-slurried with 2280 gm of DM water and was kept in autoclave at 200° C. for 6 hrs. Bring down the autoclave temperature to room temperature and filtered the material. The wet cake obtained was then dried in oven for 6 hrs to form boehmite alumina.
5.2 Preparation of phosphated boehmite alumina: 606.06 gm of this boehmite alumina (LOI=34) prepared under step 5.1 was dispersed in 800 gm of DM water and 60.68 gm of phosphoric acid (85%) was added to it. The phosphated boehmite alumina slurry was then stirred for 2 hrs.
5.3 Preparation of alumina gel: 259.74 gm of Pural 400 grade alumina (LOI: 23 wt %) was dispersed in 600 gm of DM water under stirring and milled for minimum 3 hrs. 20 gm of formic acid (85 wt %) was diluted with 100 gm of DM water and was added to alumina-DM water mixture under stirring. Mixture was kept for 20 minutes to form alumina gel.
5.4 Preparation of Clay Phosphate slurry: 235.29 gm of clay (LOI=15 wt %) was dispersed in 258 gm of DM water containing 5 gm of sodium-hexameta phosphate dispersant. To this 60.68 gm of phosphoric acid (85 wt %) under stifling was added and aged for minimum 60 min to form clay-phosphate slurry.
5.5 Preparation of final catalyst precursor slurry: Alumina gel obtained under 5.3 was added to the clay-phosphate slurry obtained under step 5.4, under vigorous stifling followed by addition of 333.33 gm of ammonium polysilicate (LOI=70 wt %) to form silica-alumina-clay-phosphate-slurry. Finally, phosphated boehmite alumina as prepared under 5.2 was added to this silica-alumina-clay-phosphate-slurry to form the final catalyst additive slurry.
5.6 Spray drying: Catalyst precursor slurry obtained under step 5.5 was spray dried with spray drier inlet temperature 360° C., out let temperature 125° C. and feed pressure of 2-4 kg/cm2.
5.7 The spray dried product obtained under step 5.6 was calcined in the furnace at a temperature of 550° C. for 1 hr to produce the final catalyst additive product.
6.1 Preparation of boehmite alumina: Initially alumina trihydrate was calcined at 550° C. for 1 hr to produce a chi-phase alumina. 550 gm of chi-phase alumina was re-slurried with 3135 gm of DM water and was kept in autoclave at 200° C. for 6 hrs. Bring down the autoclave temperature to room temperature and filtered the material. The wet cake obtained was then dried in oven for 6 hrs to form boehmite alumina.
6.2 Preparation of phosphated boehmite alumina: 833.33 gm of this boehmite alumina (LOI=34) prepared under step 6.1 was dispersed in 700 gm of DM water and 60.68 gm of phosphoric acid (85%) was added to it. The phosphated boehmite alumina slurry was then stirred for 2 hrs.
6.3 Preparation of alumina gel: 129.87 gm of Pural 400 grade alumina (LOI: 23 wt %) was dispersed in 300 gm of DM water under stirring and milled it for minimum 3 hrs. 10 gm of formic acid (85 wt %) was diluted with 100 gm of DM water and was added to alumina-DM water mixture under stifling. Mixture was kept for 20 minutes to form alumina gel.
6.4 Preparation of Clay Phosphate slurry: 176.47 gm of clay (LOI=15 wt %) was dissolved in 195 gm of DM water containing 5 gm of sodium-hexameta phosphate dispersant. To this 60.68 gm of phosphoric acid (85 wt %) under stirring was added and aged for minimum 60 min to form clay-phosphate slurry.
6.5 Preparation of final catalyst precursor slurry: Alumina gel obtained under 6.3 was added to the clay-phosphate slurry obtained under step 6.4, under vigorous stifling followed by addition of 333.33 gm of ammonium polysilicate (LOI=70 wt %) to form silica-alumina-clay-phosphate-slurry. Finally, phosphated boehmite alumina as prepared under 6.2 was added to this silica-alumina-clay-phosphate-slurry to form the final catalyst additive slurry.
6.6 Spray drying: Catalyst precursor slurry obtained under step 6.5 was spray dried with spray drier inlet temperature 360° C., out let temperature 125° C. and feed pressure of 2-4 kg/cm2.
6.7 The spray dried product obtained under step 6.6 was calcined in the furnace at a temperature of 550° C. for 1 hr to produce the final catalyst additive product.
Properties of feed where all the above additives prepared as per examples-1 to 5 are evaluated are given below Table-1:
Performance and physicochemical properties of residue up-gradation additive prepared by the above Examples-1 to 6 are shown in Table-2 & 3
| Number | Date | Country | Kind |
|---|---|---|---|
| 2970/MUM/2014 | Sep 2014 | IN | national |
