PROCESS TO PRODUCE AROMATICS OF LOW ACID-WASH COLOR

Abstract: This invention relates to Nitration Grade benzene made from a benzene stream with impurities including olefins by first fractionally distilling the benzene to a purity of at least 99 mole percent and subsequently passing the stream in a liquid phase in the presence of hydrogen through a hydrogenation step with a palladium catalyst under conditions such that substantially all olefins remaining in the stream are hydrogenated to paraffins.

Description: PROCESS TO PRODUCE AROMATICS OF LOW ACID-WASH COLOR The present invention relates to the art of producing a purified grade of benzene. Benzene is ordinarily purified by fractional distillation. Distillation, however, cannot remove certain unsaturated impurities such as diolefins which have a boiling point very close to that of benzene. Benzene which has only been fractionally distilled does not ordinarily have an acid-wash number of 2 or less. Acid-wash color is a widely used measure of the level of unsaturated impurities in benzene. The test for acid-wash color is described in ASTM D-848-81. The test involves mixing sulfuric acid with benzene and shaking the mixture so that sulfuric acid will react with unsaturated impurities in the benzene. The dis¬ coloration caused by the product of sulfuric acid and the unsaturated impurities is the acid-wash color, which is measured and translated into a numerical assessment of discoloration. "Nitration Grade" benzene must have an acid-wash number of 2 or less. Olefins have long been removed by passing the benzene through a clay treatment bed. The purification processes using clay treatment beds are described in several U.S. patents: Fukuda et al., Production of High Purity Benzene from Cracked Petroleum Residues, U.S. Patent 3,400,168 (September 3, 1968); Davis, Purification of Aromatic Hydrocarbons, U.S. Patent 3,485,884 (December 23, 1969); Ehrlich et al., Hydrodealkylation, U.S. Patent 3,754,045 (August 21, 1973); Vickers, Aromatics Extraction and Distillation Process, U.S. Patent 4,070,408 (January 24, 1978); and Takahashi et al., Process for Producing High Purity Benzene, U.S. Patent 4,247,729 (January 27, 1981). Clay beds are very inefficient from an industrial standpoint. They operate at high temperatures and high back pressures, are toxic hazards for persons exposed to the spent clay, and cannot be regenerated so that used clay must be landfilled in an environmentally sound manner. Recent patents have also suggested that olefins can be removed by passing benzene over a hydrogenation catalyst with hydrogen prior to fractional distil- lation. In that manner, olefin impurities are hydro- genated to paraffins, which are easier to distill from the benzene. Patents which have discussed such a process include: Love et al., Production of Hydro¬ carbon Solvents of Low Acid-Wash Color, U.S. Patent 2,731,506 (January 17, 1956); Fukuda et al., Process for Producing High Purity Benzene, U.S. Patent 3,310,592 (April 19, 1965); Nelson et al., Method for Improving the Quality of Dealkylated Aromatic Compounds, U.S. Patent 3,310,593 (March 21, 1967); Peterson et al., Method for Improving the Quality of Aromatic Compounds, U.S. Patent 3,310,594 (March 21, 1967); Home et al., Benzene from Pyrolysis Gasoline, U.S. Patent 3,625,879 (December 7, 1971); Eisenlohr et al., Production of Extra Pure Aromatics, U.S. Patent 3,869,377 (March 4, 1975); and Derrien et al., Process for Producing Benzene by Hydrodealkylation of a Hydrocarbon Fraction Comprising Alkyl-Aromatic Hydrocarbons, Olefinic Hydrocarbons and Sulfur Compounds, U.S. Patent 4, 463,206 (July 31, 1984). Foreign sources which describe catalytic hydrogenation to purify aromatic materials include: Essler, East German Patent 129,269 (published January 11, 1978); Sumitomo Chemical, Japanese Patent 52/136,205 (pub¬ lished November 14, 1977); and Mitsui Toatsu Chemical, Inc., Japanese Patent 60/185,733-A (published Septem¬ ber 21, 1985). Those processes may effectively remove olefin impurities from benzene. However, other impurities found in the benzene can deactivate the catalyst, necessitating frequent replacement of the catalyst. Furthermore, such processes may be wasteful of energy. The benzene must ordinarily be heated up to a tempera¬ ture appropriate for a gas-phase hydrogenation, then cooled back to a liquid phase to prepare for fractional distillation, and then heated and cooled again in the distillation process. What is needed is a process to purify benzene and drive its acid-wash color down to 2 or less without generating substantial amounts of environmentally hazardous by-products and without the need to repeatedly heat the benzene to a gas phase and then cool it to a liquid phase. The present invention is a process to produce an aromatic liquid with an acid-wash color of two or less, wherein a stream comprising primarily a liquid aromatic compound with some impurities which include olefins is first fractionally distilled to a purity of at least about 99 percent by weight and is subsequently passed in a liquid phase over a hydrogenation catalyst with a sufficient amount of hydrogen and under conditions such that substantially all olefins in the stream are hydrogenated to paraffins, but little aromatic liquid is hydrogenated. Surprisingly, when an aromatic stream is fractionally distilled before hydrogenation rather than after, according to the process of the instant invention, the aromatic liquid produced is Nitration Grade, the hydrogenation catalyst is protected from deactivating impurities, and the process can be maintained in preferred embodiments without repeated heating and cooling of the aromatic stream. The liquid aromatic compound to be treated by the instant process may be benzene, toluene, or other aromatic compound-s which must " meet standards for Nitration Grade solvents. Preferably, the compound to be purified by the present invention is benzene, and the stream which is to be treated according to the instant process comprises at least 85 percent benzene by weight. More preferably, the stream comprises at least 97 percent benzene. Preferably, the impurities in the benzene stream comprise toluene equal to 2 to 14 percent of the whole stream and naphthalene, biphenyl, and olefin impurities equal to 1 to 13 percent of the stream. Most preferably, the benzene stream is product from the hydrodealkylation of toluene or other alkyl- -substituted aromatic compounds. Such processes are well known in the art and are described in Home, Benzene from Pyrolysis Gasoline, U.S. Patent 3,625,879 (December 7, 1971) and Derrien et al., Process for Producing Benzene by Hydrodealkylation of a Hydrocarbon Fraction Comprising Alkyl-Aromatic Hydrocarbons, Olefinic Hydrocarbons and Sulfur Compounds, U.S. Patent 4,463,206 (July 31, 1984). Preferably, the aromatic stream is fractionally distilled in a two step process. First, the stream passes through a stabilization column to remove components lighter than the desired aromatic liquid. When the desired liquid is benzene, the temperature of benzene in the stabilization column is preferably at least 100°C, more preferably at least 115°C, and preferably at most 160°C, ' more preferably at most 145°C. Pressures in the column are preferably at least 70 psig (480 kPa gauge), more preferably at least 115 psig (790 kPa gauge), and preferably at most 290 psig (2000 kPa gauge), more preferably at most 220 psig (1500 kPa guage). Light impurities in the benzene preferably come out overhead at 100°C, whereas bottoms from the first step preferably come out at 150°C to 200°C. The composition of the bottoms is often little changed from that of the stream entering the first step, since light components are not a major part of the stream. Second, the aromatic stream passes through a fractionating column, also known in the art as a finishing column, under conditions generally known in the art, in order to distill the aromatic liquid to a purity of 99+ percent. When the desired product is benzene, the bottoms from the stabilization column are cooled to preferably at lea.st 90°C, more preferably at least 110°C, and preferably at most 175°C, more preferably at most 150°C. The maximum pressure in the column is preferably 30 psig (205 kPa gauge), more preferably 14.5 psig (100 kPa gauge). The minimum pressure in the column is preferably 2.2 (15 kPa gauge). The maximum temperature of aromatic ' compound which comes out of the column overhead is preferably 120°C, more preferably 90°C, and most preferably 80°C. The minimum temperature is preferably 20°C, more preferably 55°C, and most preferably 75°C. It is preferred that a condenser liquefy the aromatic compound and a reflux pump raise the pressure of the aromatic stream to 50 to 100 psig (345 to 690 kPa gauge). Preferably, part of the finished stream may be sent back to the finishing column for further reflux. Upon leaving the finishing column and going on to the third step, the aromatic liquid is preferably at least 99 percent pure by weight and more preferably at least 99.9 percent pure by weight, with olefins comprising a major impurity. Preferably, the acid-wash color of the aromatic liquid is no more than 8, and more preferably no more than 4. The third step of the present invention com¬ prises catalytically hydrogenating olefin impurities in the stream by passing the distilled stream admixed with hydrogen over a hydrogenation catalyst bed. Catalysts and the condition for their use are well known in the art. The catalyst pre * ferably comprises palladium. Palladium on a metal oxide . support is highly preferred. More preferably, the catalyst comprises 0.05 to 1 percent palladium. Most preferably, the catalyst comprises 0.05 to 0.5 percent palladium. The support is more preferably particulate alumina. The supported catalyst most preferably has a surface area of 35 m 2 per gram. The hydrogen may be pure hydrogen gas or hydrogen in an inert diluent such as methane. Preferably, the molar ratio of aromatic compound to hydrogen is between 1:1.5 and 1000:1, depending upon the amount of olefin in the aromatic stream. More preferably, the concentration of hydrogen in the hydrogenation step is enough to completely saturate all. olefin impurities without leaving an unnecessary excess of hydrogen gas. The aromatic stream may flow cocurrently or countercurrently with the hydrogen stream. The minimum pressure during hydrogenation is preferably 30 psig (205 kPa gauge). The maximum pressure during hydrogenation is preferably 500 psig (3500 kPa gauge), and more preferably 100 psig (700 kPa gauge). Most preferably, the pressure is the pressure at which the aromatic stream leaves the reflux pump (50 to 100 psig (350 to 700 kPa gauge)). The temperature of the catalytic hydrogenation step is preferably at least 20°C and more preferably " at least 40°C, preferably at most 130°C and more preferably at most 90°C. Most preferably, the temperature of the hydrogenation step is approximately the temperature at which the aromatic stream comes off of the finishing column (described previously) . The hydrogenation takes place in a liquid-phase reaction, preferably with a residence time of at least 2 minutes. More preferably, the residence time is at most 40 minutes, and most preferably the residence time is at most 5 minutes. After leaving the catalytic hydrogenation step, the aromatic liquid passes through a flash drum, small column or other known means to remove excess hydrogen gas in order to prevent an explosion hazard in storage. Benzene purified according to the present invention has an acid-wash color of less than 2, preferably less than 1 , and is ready for storage and sale as "nitration grade" benzene without further refinement. The remaining impurities do not substantially affect the acid-wash number. In its preferred embodiments, the present purification process only requires that the benzene stream be heated once and utilizes the heat remaining in the stream thereafter. Furthermore, in the present process, impurities which are harmful to the catalyst are removed from the benzene stream upstream from the catalytic hydrogenation step, so that those impurities do not harm the catalyst. The following examples illustrate the proper functioning of the instant process, but are not intend¬ ed to limit the scopes of either the specification or the claims. Example 1 A 6"x2' (150 mm x 609 mm) catalyst bed was prepared, using a catalyst of 0.3 percent palladium by weight on alumina (surface area approximately 35 m 2 per gram). A stream comprising 85 percent hydrogen and 15 percent methane by mole was passed over the catalyst at 8θ°C for " a few hours to ensure that the catalyst was fully reduced. When the catalyst was ready, 0 distillation of the benzene stream started and the hydrogen stream was left running. First, effluent from a hydrodealkylation C . process for making benzene was cooled through heat exchangers to 60°C at a pressure of 450 psig (3100 kPa gauge) and passed through a flash drum where gaseous impurities were removed. Second, it entered a stabilization column at 130°C and at a pressure of 175 0 psig (1206 kPa gauge). Third, bottoms from the stabilization column were cooled in a heat exchanger to 125°C and passed into a finishing column at 5 psig (35 kPa gauge). Overheads were passed through a condenser and a reflux pump which liquefied the benzene and increased the pressure to 50 psig (350 kPa gauge) at a temperature of 55°C. About half of the overheads were sent back to the finishing column for further reflux and the rest proceeded on to the catalyst bed. 0 Overheads proceeding to the catalyst bed were 99.93 percent benzene by mole and had an acid-wash color of about 4. They passed through the catalyst bed cocurrently with the hydrogen/methane stream over a residence time of 10.2 'minutes. The molar ratio of benzene to hydrogen was 25CL: 1. After leaving the catalyst bed, the benzene passed through a flash drum to remove excess hydrogen. The acid-wash color of the benzene was less than 1. Example 2 The same procedure as example 1 was followed, except that the temperature of benzene entering the catalyst bed was 100°C and the pressure was 100 psig. The acid-wash color of the benzene produced was less than 1. Example 3 The same procedure as example 2 was followed, except that the residence time in the catalyst bed was 2.5 minutes. The acid-wash color of the benzene produced was less than 1. Example 4 The same procedure as Example 1 was followed, except that the benzene stream passed through the catalyst bed at a temperature of 100°C for a residence time of 2.5 minutes. The acid-wash color of the benzene produced was less than 1. Example 5 The same procedure as Example 1 was followed, except that the molar ratio of benzene to hydrogen was 1000:1. The acid-wash color of the benzene produced was less than 1. Example 6 The same procedure as Example 5 was followed, except that the residence time of the benzene in the catalyst bed was 2.5 minutes. The acid-wash color of the benzene produced was less than 1. Example 7 The procedure of Example 1 was followed, except that the benzene passing into the catalyst bed had an acid-wash color of 8, a pressure of 40 psig (20 kPa gauge), and a temperature of 25°C; the benzene to hydrogen molar ratio was 0.83:1; and the benzene passed over the catalyst for a residence time of 10.2 minutes. The resulting benzene had an acid-wash color of less than 1. Example 8 The procedure of Example 1 was followed, except that the benzene passing into the catalyst bed had an acid-wash color of 8, a pressure of 155 psig (1070 kPa gauge), and a temperature of 44°C; the hydrogen was a stream of 99+ percent by mole hydrogen and the benzene to hydrogen molar ratio was 1.67:1; and the benzene passed over the catalyst bed for 20 minutes. The resulting benzene had an acid-wash color of less than 1.

Claims: CLAIMS : 1. A process to produce an aromatic liquid with an acid-wash color of two or less from a stream containing primarily aromatic liquid with impurities which include olefins, said process comprising the steps of: (1) fractionally distilled said stream such that the purity of said aromatic liquid is increased to at least 99 percent by weight; and (2) passing said stream after said 0 distillation step in a liquid phase over a hydrogenation catalyst with a sufficient amount of hydrogen and under conditions such that substantially all olefins remaining in the stream are hydrogenated T5 to paraffins, but little aromatic liquid is hydrogenated. 2. The process of Claim 1 wherein the catalyst comprises palladium on a metal oxide support. 20 3. The process of Claim 2 wherein the catalyst comprises from 0.05 to 1 percent palladium by weight on a metal oxide support, and the aromatic liquid is benzene. 25 4. A process as claimed in Claim 3 wherein hydrogenation takes place at a temperature of 20°C to 130°C and a pressure of 30 to 100 psig (205 to 700 kPa gauge) . 5. A process as claimed in Claim 4 wherein the benzene leaving the fractional distillation and going to the hydrogenation step is about 99.9 mole percent benzene or more.. 6. A process as claimed in Claim 5 wherein the hydrogenation step takes place at approximately the temperature at which the benzene leaves the fractional distillation step. 7. A process as claimed in Claim 6 wherein the catalyst comprises from 0.05 to 0.5 percent palladium by weight on alumina. 8. A process as claimed in Claim 6 wherein the hydrogenation step takes place at a temperature of from 40°C to about 90°C. 9. A process as claimed in Claim 1 wherein the stream comprising primarily benzene is effluent from a hydrodealkylation process. 10. A process as claimed in Claim 1 wherein said aromatic liquid is benzene, toluene or another aromatic compound which must ordinarily meet standards for Nitration Grade solvents.

Inventors: DURHAM GEORGE RICHARD, HEBERT RANDY STEVENS, DURHAM, GEORGE, RICHARD, HEBERT, RANDY, STEVENS
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1988
Main classification: C07C7
IPC codes: B01J23, C07B61, C07C7, C07C15