Ethylene from cracking

In a plant producing 200 kt/a of ethylene from cracked naphtha, acetylene in the product was hydrogenated to ethylene in a catalytic unit operated under conditions mild enough not to hydrogenate ethylene. During a temporary shut-down and probably owing to operating error, the internal temperature in the catalytic unit rose to... 

Gas Absorption. Oil absorption may be used for the separation of ethylene from cracked gases, as outlined by Kniel and Slages (47). Absorption in cuprous salt solutions may also be used for the extraction of ethylene from gas streams, as outhned by Sergeys (74). 

The Wacker process, the oxidation of ethylene to acetaldehyde, lost its original importance over the past 30 years. While at the beginning more than 40 factories with a total capacity of more than 2 million tons of acetaldehyde per year were installed, acetaldehyde as an industrial intermediate was replaced successively by other processes. For example, compounds such as butyraldehyde/butanol are produced by the oxo process from propylene, and acetic acid by the Monsanto process from methanol and CO or by direct oxidation of ethane. The way via acetaldehyde to these products is dependent on the price of ethylene. Petrochemical ethylene from cracking processes became considerably more expensive during these years. Thus, only few factories would be necessary to meet the demand for other derivatives of acetaldehyde such as alkyl amines, pyridines, glyoxal, and pentaerythritol. 

Ethylene from cracking of the alkane gas mixtures or the naphtha fraction can be directly polymerized or converted into useful monomers. (Alternatively, the ethane fraction in natural gas can also be converted to ethylene for that purpose). These include ethylene oxide (which in turn can be used to make ethylene glycol), vinyl acetate, and vinyl chloride. The same is true of the propylene fi action, which can be converted into vinyl chloride and to ethyl benzene (used to make styrene). The catalytic reformate has a high aromatic fi action, usually referred to as BTX because it is rich in benzene, toluene, and xylene, that provides key raw materials for the synthesis of aromatic polymers. These include p-xylene for polyesters, o-xylene for phthalic anhydride, and benzene for the manufacture of styrene and polystyrene. When coal is used as the feedstock, it can be converted into water gas (carbon monoxide and hydrogen), which can in turn be used as a raw material in monomer synthesis. Alternatively, acetylene derived from the coal via the carbide route can also be used to synthesize the monomers. Commonly used feedstock and a simplified diagram of the possible conversion routes to the common plastics are shown in Figure 2.1. 

Although ethylene is produced by various methods as follows, only a few are commercially proven thermal cracking of hydrocarbons, catalytic pyrolysis, membrane dehydrogenation of ethane, oxydehydrogenation of ethane, oxidative coupling of methane, methanol to ethylene, dehydration of ethanol, ethylene from coal, disproportionation of propylene, and ethylene as a by-product. 

The olefins used are propylenes and butylenes ethylene is also produced from cracking operations but is not used in refinery processing. 

The use of methane, ethane, ethylene, propylene, and propane pure light hydrocarbons as refrigerants is quite common, practical, and economical for many hydrocarbon processing plants. Examples include ethylene manufacture from cracking some feedstock, ethylene or other hydrocarbon recycle purification plants, gas-treating plants, and petroleum refineries. 

Chemicals directly based on propane are few, although as mentioned, propane and LPG are important feedstocks for the production of olefins. Chapter 6 discusses a new process recently developed for the dehydrogenation of propane to propylene for petrochemical use. Propylene has always been obtained as a coproduct with ethylene from steam cracking processes. Chapter 6 also discusses the production of aromatics from LPG through the Cyclar process. ... 

Like ethylene, propylene (propene) is a reactive alkene that can be obtained from refinery gas streams, especially those from cracking processes. The main source of propylene, however, is steam cracking of hydrocarbons, where it is coproduced with ethylene. There is no special process for propylene production except the dehydrogenation of propane. 

A typical ethane cracker has several identical pyrolysis furnaces in which fresh ethane feed and recycled ethane are cracked with steam as a diluent. Figure 3-12 is a block diagram for ethylene from ethane. The outlet temperature is usually in the 800°C range. The furnace effluent is quenched in a heat exchanger and further cooled by direct contact in a water quench tower where steam is condensed and recycled to the pyrolysis furnace. After the cracked gas is treated to remove acid gases, hydrogen and methane are separated from the pyrolysis products in the demethanizer. The effluent is then treated to remove acetylene, and ethylene is separated from ethane and heavier in the ethylene fractionator. The bottom fraction is separated in the deethanizer into ethane and fraction. Ethane is then recycled to the pyrolysis furnace. 

As a general rule difficult or expensive separations should be performed last, since by that time less total material will be involved. Consider Table 4-1, which gives the product mix obtained in a cracking furnace of an ethylene plant and the normal boiling points of the compounds. Suppose it is desired to separate the six groups listed in the table using distillation. The separation of ethylene from ethane and propylene from propane will be the most difficult because they have the smallest boiling-point differences. Therefore, these steps should be performed last. 

Referring to the hardware in Figure 5—4, there are much larger facilities required for heavier liquids cracking than for ethane or propane. As you saw in Table 5—1, the yield of ethylene from the heavier feeds is much lower than from ethane. That means that to produce the same amount of ethylene on a daily basis, the gas-oil furnaces have to handle nearly five times as much feed as ethane furnaces. As the design engineer scales up these volumes, he or she has to worry about the size of the cubes necessary to heat up that much feed, the residence times best for each kind of feed, and the best pressure/temper-ature/steam mixture conditions. 

VC is made by cracking EDC in a pyrolysis furnace much like that in an ethylene plant. Thats one of the three reactions, shown in Figure 9—1, involved in the process. The other two have formidable names—chlorination and oxychlorination—but simple enough reactions—the addition of chlorine and the addition of oxygen and chlorine. What is a little complicated is the fact that the hydrogen chloride used to make the EDC in the first reaction comes from cracking EDC in the second. Sounds like a closed circle until you peel it back and examine it. 

The dry gas prodnced from the DCC process contains approximately 50% ethylene. The cracking reactions are endothermic, and compared to FCC, a higher coke make is required to satisfy the heat balance. 

Recovery of ethylene and acetylene from cracked hydrocarbon gases... 

Prior to this time, other ventures had already been operating to produce commercial quantities of aliphatic chemicals from petroleum sources. Truly commercial production of ethylene glycol had been achieved by 1925 (10) using natural gas fractions as a starting material, and even earlier (about 1920) there had been the manufacture of isopropyl alcohol from cracking plant propylene (20), which may be termed the pioneer operation on a successful, continuing basis in the sphere of aliphatic synthesis from petroleum. 

Figure 17.15. A fired heater as a high temperature reactor, (a) Arrangement of tubes and burners (1) radiant tubes (2) radiant panel burners (3) stack (4) convection chamber tubes (Sukhanov, Petroleum Processing, Mir, Moscow, 1982). (b) Radiant (surface-combustion) panel burner (1) housing (2) ceramic perforated prism (3) tube (4) injector (5) fuel gas nozzle (6) air throttle Sukhanov, Petroleum Processing, Mir, Moscow, 1982). (c) Fired tubular cracking furnace for the preparation of ethylene from naphtha.

Symmes, in a footnote, p. 375, in his English translation of Naoum s book, op. cit., cites U. S. patents 1,307,032, 1,307,033, 1,307,034, and 1,371,215 which describe a method for the manufacture of mixed ethylene and propylene glycols from cracking gas, satisfactory methods for the nitration of the mixture and for the stabilization of the mixed nitric esters, and explosives made from the products which practical tests in actual use showed could not be frozen even at temperatures prevailing in winter along the Canadian border, or —10° to —30° F. ... 

Newer catalysts of the fluoride type promise to be much more versatile. Essentially all ethylene from catalytic cracking was once burned as fuel but can now be utilized for the production of ethylbenzene using newer catalysts. 

Figure 2 shows the effect of cracking temperature at 2 s vapor residence time on the yields of BTX, benzene, and ethylene from Linby coal (A), coal extract (B), and anthracene oil (C). 

Nowadays, it is believed worldwide that n-paraffins, which are extracted from kerosene, will be more advantageous raw material than ethylene from naphtha cracking in view of both resource saving and process economics. 

RECOVERY OF ETHYLENE-RICH DEMETHANIZER FEED LIQUID STREAMS FROM CRACKED GAS FEED... 

Ethylene (Ethene or Elayl), H2C CH2 mw 28.05 colorless, flammable, dangerous to handle gas with characteristic sweet odor and taste sp gr 0.975 (air = 1.0), mp —169.4°, bp —103.8°, flash p —136°C explosive limits in air, % by vol, lower 3.0 upper 34.0 si sol in w, more in ale sol in eth. Ethylene is a major component of petroleum refinery gas from cracking units, and is sometimes recovered therefrom by distillation or other means. Some pure ethylene is produced by passing hot ethanol vapors over a catalyst, such as activated alumina (Ref 4). Its laboratory prepn consists of heating ethanol in definite proportions with sulfuric acid of certain concns. By using a 90% acid and 90% ale, ethylene can be produced in a regular stream at a yield of 84 to 85% of theory (Ref 2). 

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