Claim of Priority

[0001] This application claims priority to U.S. Patent Application No. 16/899,254 filed on June 11, 2020, the entire contents of which are hereby incorporated by reference.

Background

[0002] The polymerization of olefins often uses comonomers to affect the final properties, such as density, crystallinity, and the like. The comonomers are generally alpha-olefins, such as 1 -butene, 1 -hexene, and 1-octene, among others. Alpha-olefins are also important feedstocks for numerous other products, including additives for drilling fluids, lubricants, synthetic oils, plasticizers, and other products.

[0003] One of the most important alpha-olefins is 1 -butene. The market size projection for 1-butene has been projected to pass four billion USD in 20210. Satisfying the projected demand for 1 -butene through the currently used method of ethylene dimerization may be impractical due to costs and its competitive use in polyethylene.

Summary

[0004] An embodiment described herein provides a method for using red mud as a catalyst for isomerization of olefins. The method includes calcining the red mud, flowing an olefin feedstock over the red mud in an isomerization reactor, and separating an alpha-olefin from a reactor effluent.

[0005] An embodiment described herein provides an isomerization unit for producing an alpha-olefin product stream from an olefin feedstock. The isomerization unit includes an upstream purification system to separate a feed stream that comprises olefins from an initial feedstock, generating the olefin feedstock. The isomerization unit includes a reactor comprising a red mud catalyst to isomerize the olefins to form an alpha-olefin and a product purification system to isolate the alpha olefin product stream from an effluent from the reactor.

Brief Description of Drawings

[0006] Figure 1 is reaction scheme showing the inter-conversions of 2-butene and 1 -butene by isomerization. [0007] Figure 2 is a method 200 for using a red mud catalyst to isomerize olefins in a feedstock to alpha-olefins.

[0008] Figure 3 is an isomerization unit 300 for producing an alpha-olefin from an olefin feedstock, using a red mud catalyst. [0009] Figure 4 is a schematic diagram of an experimental tube reactor 400 for testing the conversion of 2-butene to 1 -butene using a red mud catalyst.

[0010] Figure 5 is a bar chart showing the comparative yield of three catalysts in the conversion of 2-butene to 1 -butene.

[0011] Figure 6 is a reaction scheme 600 showing the formation of hydrocarbon contaminants from the reaction of 1 -butene and 2-butene.

[0012] Figures 7A-7C are bar charts showing the comparative selectivity of three catalysts in the conversion of 2-butene to 1 -butene.

Detailed Description

[0013] One method for the production of alpha-olefins is the isomerization of, which is an available material in refineries. The isomerization proceeds with aid of catalysts, such as SiC , TiCb, organo-aluminum, or zinc chromium ferrite (ZnxCr _y Fe _z 04), acidized clay, alumina, or MgO catalysts, among others. However, research into low cost, durable, selective and efficient catalysts is still needed.

[0014] Methods for the use of red mud as a catalyst for the isomerization is described herein. Red mud is a waste product generated during alumina production in the Bayer process, which is responsible for more than 95% of all alumina produced in the world. In this process, each ton of aluminum oxide that is produced results in 0.3 to 2.5 tons of bauxite tailings, or red mud. As a consequence, about 155 million tons of red mud are created annually with worldwide storage at over 3.5 billion tons in 2014. Accordingly, red mud is a low cost material that is in high supply. Although red mud has significant heterogeneity, the generic composition is shown in Table 1. The complex mixture of metals indicates that red mud may be an effective catalyst for the isomerization of olefins, such as 2-butene to 1 -butene described in examples herein.

Table 1: The generic composition of global red mud [0015] Figure 1 is reaction scheme 100 showing the inter-conversions of 2-butene and 1 -butene by isomerization. In the reaction scheme 100, trans-2-butene 102, cis-2- butene 104, and 1 -butene 106 can be isomerized to each other. The lowest energy configuration is the trans-2-butene 102, and, thus, a catalyst is used to form the 1- butene 106. Similar interconversions may be used in the isomerization of other olefins. [0016] As described herein, red mud is used as the catalyst to isomerize the 2- butene isomers 102 and 104 to produce 1 -butene. This takes advantage of the mixture of metals constituting red mud, which include Ti, Fe and Al. The mixture of the metal compounds in the red mud may enhance the isomerization yield and selectivity, for example, as compared to MgO or SiC catalysts. Further, red mud is a waste material of negligible cost, which improves the competitive advantage over synthesized catalysts containing MgO or SiC . Accordingly, even at comparable rates of isomerization yield and selectivity, the low cost of the red mud makes its use favorable over higher cost catalysts.

[0017] Figure 2 is a method 200 for using a red mud catalyst to isomerize olefins in a feedstock to alpha-olefins. In an embodiment, the method 200 is used to isomerize 2-butenes to 1 -butene.

[0018] The method 200 begins at block 202, with loading the catalyst into the reactor. At block 204, the catalyst is prepared and activated. As red mud is a common waste material that is being used as supplied, the preparation is minimal. As described in the examples, the red mud is heated to drive off excess moisture and volatile components. The drying is performed under air at a temperature of between about 500 °C and about 800 °C, or at a temperature of between 600 °C and about 700 °C, or at about 650 °C. The drying may be performed for between about 10 minutes (min.) and about 150 min., or for between about 30 min. and about 130 min., or for about 45 min. The catalyst is further calcined for activation, for example, by the generation of surface groups. The activation may be performed under a flow of an inert gas. The activation is performed at a temperature of between about 400 °C and about 700 °C, or at a temperature of between 500 °C and about 600 °C, or at about 650 °C. The activation may be performed for between about 2 hours and about 6 hours, or for between about 3 hours and about 5 hours, or for about 4 hours.

[0019] In commercial usage, the catalyst may be dried and activated at a remote production facility, before being brought to the isomerization unit and loaded into the reactor. Any number of combinations of this may be performed. For example, the catalyst may be dried at the remote production facility and activated after being loaded into the commercial isomerization reactor.

[0020] At block 206, the olefin feedstock, such as a 2-butene feedstock, is flowed into the reactor for isomerization into the other alpha-olefins, such as 1 -butene. In some embodiments described herein, the 2-butene feedstock is a mixture of cis-2- butene and trans-2-butene, for example, at a 50-50 ratio. In various embodiments, such as in commercial usage, the 2-butene feedstock is a refinery stream that includes a number of hydrocarbons with boiling points in a range, such as a light fraction from a hydrocracking unit, for example, having a boiling point range of about -30 °C to about 40 °C, about -20 °C to about 10 °C, or about -10 °C to about 0 °C. A narrower range of boiling points may be indicative of a feedstock that is higher in cis-2-butene and trans- 2-butene, providing a higher purity 1 -butene product stream, and decreasing the purification needed downstream before sales. The butene feedstock is flowed through the reactor at a weight-hour space velocity (WHSV) (hr ^-1 ) of between about 400 hr ¹ and about 1400 hr ¹ , or between about 650 hr ¹ and about 1150 hr ¹ , or about 900 hr ¹ . [0021] At block 208, the alpha-olefin, or 1 -butene, product is separated from the reactor effluent. The alpha-olefin, or 1 -butene, may then be provided to other processes, such as polymerization of polyolefins. At block 210, the separated effluent, for example, including unreacted olefins, such as 2-butene, may be recycled to the reactor to increase yields. The separated effluent may be sent to purification systems upstream of the reactor to remove other hydrocarbons or may be provided directly to the reactor, for example, by being mixed with the initial feedstock.

[0022] Figure 3 is an isomerization unit 300 for producing an alpha-olefin from an olefin feedstock, using a red mud catalyst. In some embodiments, the isomerization unit 300 is used for producing 1 -butene from 2-butene. The isomerization unit 300 may be part of a refinery system, producing a number of different hydrocarbon streams. In this example, the isomerization unit 300 includes three units, an upstream purification system 302, a reactor 304, and a product purification system 306.

[0023] The initial feedstock 308 is fed to the upstream purification system 302. In various embodiments, the upstream purification system 302 includes a distillation column, a cryogenic distillation column, a flash vessel, and the like. Other streams (not shown), having different boiling point ranges, are separated out in the upstream purification system 302 and sent to another processing units. An isomerization feedstock stream 310, for example, having a boiling point range that includes trans-2- butene and cis-2-butene, is provided to the reactor 304.

[0024] In the reactor 304, the isomerization feedstock stream 310 is flowed over the red mud, which catalyzes the isomerization reaction of at least a portion of the olefins to an alpha-olefin product, such as catalyzing a portion of 2-butene feedstocks to a 1 -butene product. A reactor effluent stream 312 is then provided to the product purification system 306. In some embodiments, the reactor 304 is a standard isomerization reactor used in a refinery.

[0025] In the product purification system 306, the alpha-olefin product stream, such as the 1-butene product, is separated and provided as product stream 314. In various embodiments, the product purification system 306 includes a distillation column, a cryogenic distillation column, a flash vessel, and the like. The alpha-olefin product stream 314 may be sold to polyolefin manufacturers, used in other processes to form other products, and the like. Other streams (not shown) from the product purification system 306 may be sent to other processing units. In some implementations, a recycle stream 316 is returned from the product purification system 306 to the upstream purification system 302 after removal of the alpha-olefin product. In some embodiments, this may be performed to allow the recovery of unreacted trans- 2-butene and cis-2 -butene to increase the overall yield of the process. In other embodiments, the recycle stream 316 is combined with the isomerization feedstock stream 310 directly, and fed to the reactor 304.

[0026] Examples

[0027] To demonstrate the use of red mud as an isomerization catalyst, feed streams including 2-butenes were isomerized to 1 -butene. The products were analyzed to determine the yields and selectivities of the red mud catalyst.

Elemental analyses were performed by X-ray Fluorescence (XRF) analysis. The XRF analysis was performed on a Horiba® XGT-7200. The X-ray tube is equipped with an Rh target, voltage was set at 30 kV, no X-ray filter was used, and analysis preset time was 400 s. Before measurement, samples were placed on a double-sized tape (NICETACK™, Prod. No NW-15) and then placed in the chamber, which was then degassed. The results are an average of four measurements were taken. The general composition of Saudi Arabian red mud is shown in Table 2. The red mud composition listed in Table 2 is the comprehensive composition, which includes both major and minor constituents.

Table 2: Typical composition of Saudi Arabian Red Mud in weight percent.

Table 3: Composition of Experimental Saudi Arabian red mud in weight percent.

[0028] The performance of a Saudi Arabian red mud sample in the isomerization of a mixture of trans-2-butene and cis-2 -butene to 1 -butene was evaluated at different temperatures, 450°C, 500°C and 550°C. An example of an elemental composition of a Saudi Arabian red mud sample used for runs herein is shown in Table 3. The composition listed in Table 3 is only for the major constituents that are always reported in literature as red mud composition. As red mud is a waste material the composition is heterogeneous, with a 5 %, or higher, variation in the composition. This can be seen in the comparison of the Fe203 amounts in Table 2 versus Table 3. The variation in composition does not substantially affect the products or selectivity.

[0029] The results of the isomerization were compared to MgO and SiC commercial catalysts. The experimental runs were performed in a BTRS reactor unit from Autoclave Engineers division of Parker Hannifin Corp, having 9 mm ID and 30 cm length. The reactor is SS steel reactor with 4 different MFC units to control the flowing gases. Maximum capacity of the reactor system is 800 C and can withstand up to 20 bar of reaction pressure. The amount of catalyst used in each run was 2 mL (0.65 g)·

[0030] Figure 4 is a schematic diagram of an experimental tube reactor 400 for testing the conversion of 2-butene to 1 -butene using a red mud catalyst. To hold the material in place a layer of quartz wool 402 is inserted into the experimental reactor tube 400. An initial layer 404 of 14 g of silicon carbide are poured over the quartz wool 402. A catalyst layer 406 including about 2 mL of catalyst is inserted into the experimental tube reactor 400. For the red mud catalyst, the 2 mL corresponds to about 0.65 g. Finally, atop layer 408 of about 17 g of silicon carbide is poured over the catalyst layer 406. The experimental reactor tube 400 is then inserted into the BTRS catalyst testing system. Prior to evaluation each catalyst sample was calcined under air at 650 °C to remove moisture or volatile gases, if present. The catalyst sample was then activated at 550 °C inside the reactor for 4 hrs under nitrogen. The 2-butene feed is a mixture of 50 % cis-2-butene and 50 % trans-2-butene. The concentration of 2- butene employed in the evaluation was 15 % (5 ml) diluted with N2 (25 ml).

[0031] The amounts of hydrocarbons in the reactor effluent streams were measured by gas chromatography. This was performed using an Agilent GC-7890B instrument from Agilent. The column was a capillary (HP-Al/KCL (50mX0.53mmX15microns) column with an N2 stationary phase and He carrier gas. A hybrid detector including a flame ionization detector (FID) and a thermal conductivity detector (TCD) was used. The flow rate of the carrier gas was 15 ml/min. After injection, a temperature ramp from 50 °C to 170 °C over 10 min. was performed, then the temperature was held at 220 °C forl5 min., before being cooled to the starting temperature.

[0032] From the GC results, yields and selectivities were calculated by the following formulas: Yield = Conversion of butenes X Selectivity of the product (1 -butene)

Conversion=100-(CisButene Yield+TransButene Yield)

Conversion-C4 = 100 - (Cis-2-Butene Yield + Trans-2-Butene Yield)

Yield of Product

Selectivity = x 100

Conversion

In these formulas, yield represents the yield of 1 -butene through the GC Retention Factor, and the conversion of 2-butene (cis & trans 2-butene) is obtained though GC retention factor.

[0033] Figure 5 is a bar chart 500 showing the comparative yield of three catalysts in the conversion of 2-butene to 1 -butene. At all three tested temperatures, red mud provided significantly higher yield of 1 -butene than SiC . Further, red mud provided higher yield to 1-butene than MgO at 500°C and 550°C. However, at 450°C MgO was relatively better than red mud and substantially outperformed Si02.

[0034] Figure 6 is a reaction scheme 600 showing the formation of hydrocarbon contaminants from the reaction of 1 -butene and 2-butene. Like numbered items are as described with respect to Fig. 1. In the reaction scheme 600, a metathesis reaction of 1- butene with trans-2-butene forms propylene 602 and 2-methylpentene 604. This reaction proceeds in the presence of 1 -butene 102 and 2-butene 106 (cis and trans). If 2-butene is not present, it may be formed by an isomerization reaction allowing the metathesis reaction to occur. Accordingly, understanding the selectivity of the catalyst towards the formation of 1 -butene is important.

[0035] Figures 7A-7C are bar charts showing the comparative selectivity of three catalysts in the conversion of 2-butene to 1-butene. In Fig. 7A, the selectivity of the red mud isomerization of 2-butene to 1 -butene is shown. This reaction follows the reaction scheme shown in Fig. 1, without the formation of other products. In contrast, the isomerization of 2-butene to 1-butene using an SiC catalysts, shown in Fig. 7B, indicates that some amount of n-butane and a small amount of propylene were formed, in addition to far less 1 -butene. Although MgO catalysts have higher formation of 1- butene in the isomerization then for the SiC catalysts, as shown in Fig. 7C, a number of hydrocarbon byproducts were also formed. These include n-butane, propylene, Css, isobutene, and some heavy fractions

[0036] An embodiment described herein provides a method for using red mud as a catalyst for isomerization of olefins. The method includes calcining the red mud, flowing an olefin feedstock over the red mud in an isomerization reactor, and separating alpha-olefins from a reactor effluent. In an aspect, the isomerization includes forming 1 -butene from a feedstock comprising 2-butene.

[0037] In an aspect, the method includes calcining the catalyst to dry the catalyst, remove volatile gas, or both, at a temperature of between about 500 °C and about 800 °C for between about 10 minutes and about 150 minutes. In an aspect, the method includes calcining the catalyst to dry the catalyst, remove volatile gas, or both, at a temperature of between about 600 °C and about 700 °C for between about 30 minutes and about 130 minutes. In an aspect, the method includes calcining the catalyst to dry the catalyst, remove volatile gas, or both, at a temperature of about 650 °C for about 45 minutes.

[0038] In an aspect, the method includes calcining the catalyst to activate the catalyst at a temperature of between about 400 °C and about 700 °C for between about 2 hours and about 6 hours. In an aspect, the method includes calcining the catalyst to activate the catalyst at a temperature of between about 400 °C and about 700 °C for between about 2 hours and about 6 hours. In an aspect, the method includes calcining the catalyst to activate the catalyst at a temperature of about 650 °C for about 4 hours. [0039] In an aspect, the method includes obtaining the butene feedstock from an upstream purification system in a refinery. In an aspect, the method includes obtaining the butene feedstock with a boiling point range of between about -30 °C and about 40 °C. In an aspect, the method includes obtaining the butene feedstock with a boiling point range of between about -20 °C and about 10 °C. In an aspect, the method includes obtaining the butene feedstock with a boiling point range of between about - 10 °C and about 0 °C. [0040] In an aspect, the method includes flowing the butene feedstock over the red mud at a weight hour space velocity of between about 400 hr ¹ and 1300 hr ¹ . In an aspect, the method includes flowing the butene feedstock over the red mud at a weight hour space velocity of between about 650 hr ¹ and about 1150 hr ¹ . In an aspect, the method includes flowing the butene feedstock over the red mud at a weight hour space velocity of about 900 hr ¹ .

[0041] In an aspect, the method includes separating the 1 -butene from the reactor effluent in a distillation column. In an aspect, the method includes returning the reactor effluent to an upstream purification system after removal of the 1 -butene from the reactor effluent. In an aspect, the method includes combining the reactor effluent with the butene feedstock after separating the 1 -butene from the reactor effluent.

[0042] An embodiment described herein provides an isomerization unit for producing an alpha-olefin product stream from an olefin feedstock. The isomerization unit includes an upstream purification system to separate a feed stream that includes olefins from an initial feedstock, generating the olefin feedstock. The isomerization unit includes a reactor comprising a red mud catalyst to isomerize the olefins to form an alpha-olefin, and a product purification system to isolate the alpha-olefin product stream from an effluent from the reactor. In an aspect, the feed stream comprises trans- 2-butene and cis-2-butene and the alpha-olefin product stream comprises 1 -butene [0043] In an aspect, the butene feedstock has a boiling point range of about -20 °C to about 10 °C. In an aspect, the product purification system includes a distillation column configured to recycle the effluent to the upstream purification system, after removal of the 1 -butene product stream.

[0044] Other implementations are also within the scope of the following claims.