Ethylene production

ETHYLENE We discussed ethylene production in an earlier boxed essay (Section 5 1) where it was pointed out that the output of the U S petrochemi cal industry exceeds 5 x 10 ° Ib/year Approximately 90% of this material is used for the preparation of four compounds (polyethylene ethylene oxide vinyl chloride and styrene) with polymerization to poly ethylene accounting for half the total Both vinyl chloride and styrene are polymerized to give poly(vinyl chloride) and polystyrene respectively (see Table 6 5) Ethylene oxide is a starting material for the preparation of ethylene glycol for use as an an tifreeze in automobile radiators and in the produc tion of polyester fibers (see the boxed essay Condensation Polymers Polyamides and Polyesters in Chapter 20)... 

Olefins are produced primarily by thermal cracking of a hydrocarbon feedstock which takes place at low residence time in the presence of steam in the tubes of a furnace. In the United States, natural gas Hquids derived from natural gas processing, primarily ethane [74-84-0] and propane [74-98-6] have been the dominant feedstock for olefins plants, accounting for about 50 to 70% of ethylene production. Most of the remainder has been based on cracking naphtha or gas oil hydrocarbon streams which are derived from cmde oil. Naphtha is a hydrocarbon fraction boiling between 40 and 170°C, whereas the gas oil fraction bods between about 310 and 490°C. These feedstocks, which have been used primarily by producers with refinery affiliations, account for most of the remainder of olefins production. In addition a substantial amount of propylene and a small amount of ethylene ate recovered from waste gases produced in petroleum refineries. 

Since the early 1980s olefin plants in the United States were designed to have substantial flexibiHty to consume a wide range of feedstocks. Most of the flexibiHty to use various feedstocks is found in plants with associated refineries, where integrated olefins plants can optimize feedstocks using either gas Hquids or heavier refinery streams. Companies whose primary business is the production of ethylene derivatives, such as thermoplastics, tend to use ethane and propane feedstocks which minimize by-product streams and maximize ethylene production for their derivative plants. 

The process can be operated in two modes co-fed and redox. The co-fed mode employs addition of O2 to the methane/natural gas feed and subsequent conversion over a metal oxide catalyst. The redox mode requires the oxidant to be from the lattice oxygen of a reducible metal oxide in the reactor bed. After methane oxidation has consumed nearly all the lattice oxygen, the reduced metal oxide is reoxidized using an air stream. Both methods have processing advantages and disadvantages. In all cases, however, the process is mn to maximize production of the more desired ethylene product. 

The unit Kureha operated at Nakoso to process 120,000 metric tons per year of naphtha produces a mix of acetylene and ethylene at a 1 1 ratio. Kureha s development work was directed toward producing ethylene from cmde oil. Their work showed that at extreme operating conditions, 2000°C and short residence time, appreciable acetylene production was possible. In the process, cmde oil or naphtha is sprayed with superheated steam into the specially designed reactor. The steam is superheated to 2000°C in refractory lined, pebble bed regenerative-type heaters. A pair of the heaters are used with countercurrent flows of combustion gas and steam to alternately heat the refractory and produce the superheated steam. In addition to the acetylene and ethylene products, the process produces a variety of by-products including pitch, tars, and oils rich in naphthalene. One of the important attributes of this type of reactor is its abiUty to produce variable quantities of ethylene as a coproduct by dropping the reaction temperature (20—22). 

Most by-product acetylene from ethylene production is hydrogenated to ethylene in the course of separation and purification of ethylene. In this process, however, acetylene can be recovered economically by solvent absorption instead of hydrogenation. Commercial recovery processes based on acetone, dimetbylform amide, or /V-metby1pyrro1idinone have a long history of successfiil operation. The difficulty in using this relatively low cost acetylene is that each 450, 000 t/yr world-scale ethylene plant only produces from 7000 9000 t/yr of acetylene. This is a small volume for an economically scaled derivatives unit. 

As indicated in Table 4, large-scale recovery of natural gas Hquid (NGL) occurs in relatively few countries. This recovery is almost always associated with the production of ethylene (qv) by thermal cracking. Some propane also is used for cracking, but most of it is used as LPG, which usually contains butanes as well. Propane and ethane also are produced in significant amounts as by-products, along with methane, in various refinery processes, eg, catalytic cracking, cmde distillation, etc (see Petroleum). They either are burned as refinery fuel or are processed to produce LPG and/or cracking feedstock for ethylene production. 

Production of maleic anhydride by oxidation of / -butane represents one of butane s largest markets. Butane and LPG are also used as feedstocks for ethylene production by thermal cracking. A relatively new use for butane of growing importance is isomerization to isobutane, followed by dehydrogenation to isobutylene for use in MTBE synthesis. Smaller chemical uses include production of acetic acid and by-products. Methyl ethyl ketone (MEK) is the principal by-product, though small amounts of formic, propionic, and butyric acid are also produced. / -Butane is also used as a solvent in Hquid—Hquid extraction of heavy oils in a deasphalting process. 

Ethyleneamines are used in certain petroleum refining operations as well. Eor example, an EDA solution of sodium 2-aminoethoxide is used to extract thiols from straight-mn petroleum distillates (314) a combination of substituted phenol and AEP are used as an antioxidant to control fouling during processing of a hydrocarbon (315) AEP is used to separate alkenes from thermally cracked petroleum products (316) and TEPA is used to separate carbon disulfide from a pyrolysis fraction from ethylene production (317). EDA and DETA are used in the preparation and reprocessing of certain... 

Absolute = 1.72 bar. Hydrocracked vacuum gas oil. Maximized ethylene product. Nonaromatic. 

Ethylene as a By-Product. The contribution to world ethylene production is small, but not zero. In petroleum refining fluid catalytic cracking (FCC) units, small amounts of ethylene are produced but generally not recovered, except in a few locations where large FCC units are adjacent to petrochemical faciUties. 

A. A. Lemonidou and co-workers, "Catalyst Evaluation and Kinetic Study for Ethylene Production," paper presented atMIChE SpringNational... 

Petrochemical units generate waste waters from process operations such as vapor condensation, from cooling tower blowdown, and from stormwater runoff. Process waste waters are generated at a rate of about 15 cubic meters per hour (m /hr), based on 500,000 tpy ethylene production, and may contain biochemical oxygen demand (BOD) levels of 100 mg/1, as well as chemical oxygen demand (COD) of 1,500 to 6,000 mg/1, suspended solids of 100 to 400 mg/1, and oil and grease of 30 to 600 mg/1. Phenol levels of up to 200 mg/1 and benzene levels of up to 100 mg/1 may also be present. 

The Cj plus bottoms from the demethanizer then go to the deethanizer. A propylene-propane bottoms product containing 90-92% propylene is obtained which may either be sold, used directly as propylene- 90, or further purified. The ethylene-ethane overhead from the deethanizer is separated in the splitter tower yielding a 99.8% overhead ethylene product at -25°F. The ethane bottoms at -l-18°F may either be sent to fuel gas or used as feed to an ethane cracking furnace. Overall ethylene recovery in these facilities is about 98%. The product is of very high purity with less than 50 parts per million of non-hydrocarbon contaminants and a methane plus ethane level below 250 ppm. 

One illustrative example is presented in tliis final cliapter. It lias been adopted from tlie outstanding work of Kavianaian et al. and is concerned with an ethylene production plant. Tlie solution involves a prcliminaiy hazards analysis (PHA) and tlie development of a fault tree for tlie process. 

TABLE 21.7.1 Hazard and Toxic Properties of Materials in Ethylene Production ... 

Ethylene is a constituent of refinery gases, especially those produced from catalytic cracking units. The main source for ethylene is the steam cracking of hydrocarbons (Chapter 3). Table 2-2 shows the world ethylene production by source until the year 2000. U.S. production of ethylene was approximately 51 billion lbs in 1997. ... 

Butylenes (butenes) are by-products of refinery cracking processes and steam cracking units for ethylene production. 

Butadiene is obtained mainly as a coproduct with other light olefins from steam cracking units for ethylene production. Other sources of butadiene are the catalytic dehydrogenation of butanes and butenes, and dehydration of 1,4-butanediol. Butadiene is a colorless gas with a mild aromatic odor. Its specific gravity is 0.6211 at 20°C and its boiling temperature is -4.4°C. The U.S. production of butadiene reached 4.1 billion pounds in 1997 and it was the 36th highest-volume chemical. ... 

As feedstocks progress from ethane to heavier fractions with lower H/C ratios, the yield of ethylene decreases, and the feed per pound ethylene product ratio increases markedly. Table 3-15 shows yields from steam cracking of different feedstocks, and how the liquid by-products and BTX aromatics increase dramatically with heavier feeds. 

The main gas feedstock for ethylene production is ethane. Propane and butane or their mixture, LPG, are also used, but to a lesser extent. They... 

Butadiene is obtained as a by-product from ethylene production. It is then separated from the C4 fraction by extractive distillation using furfural. 

The main source for ethane is natural gas liquids. Approximately 40% of the available ethane is recovered for chemical use. The only large consumer of ethane is the steam cracking process for ethylene production. 

Raw materials for obtaining benzene, which is needed for the production of alkylbenzenes, are pyrolysis gasoline, a byproduct of the ethylene production in the steam cracking process, and coke oven gas. Reforming gasoline contains only small amounts of benzene. Large amounts of benzene are further produced by hydrodealkylation of toluene, a surplus product in industry. 

However, it could be expected that the share of the latter group will rise to the same extent as the rising importance of environmental digestibility. It is very possible that in the future the C16/C18 ester sulfonates will partly replace the alkylbenzenesulfonates produced from petrochemical raw material [6,7]. N. R. Smith [8] expects the a-sulfo methyl esters to be an alternative to ethylene-based surfactants. An increase in the production of surfactants based on ethylene is problematic, because in industrial countries ethylene production is occurring at 95% of capacity and more. 

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