Bottoms recycling

Exxon was the first to investigate the suitabiUty of a wide range of different U.S. coals for conversion. Operation of the EDS process was demonstrated in a 230 t/d unit in Baytown, Texas that had a start-up in May of 1980. Data on the response of a variety of coals to once-through and bottoms recycle operations are shown in Eigure 4. Eigure 5 presents typical Hquefaction product distributions for the system operated both with and without the Elexicoking (fluidized-bed coking) option. 

Eig. 4. Product yields for EDS process on D on once-through and a bottoms recycle basis for various types of coal. DAF = dry ash free. 

FT Total column bottoms recycle flow rate... 

FTl Column bottoms recycle flow rate of component i... 

The recovery, regeneration, and repeated reuse of the active catalyst are of prime importance in substantially reducing the overall cost of coal liquefaction. The used catalysts usually remain in the bottoms products, which consist of nondistillable asphaltenes, preasphaltenes, unreacted coal, and minerals. The asphaltenes and preasphaltenes can be recycled with the catalyst in bottoms recycle processes. However, unreacted coal and minerals, if present in the recycle, dilute the catalyst and limit the amount of allowable bottoms recycle because they unnecessarily increase the slurry viscosity and corrosion problems. Hence, these useless components should be removed or at least reduced in concentration. If the catalyst is deactivated, reactivation becomes necessary before reuse. Thus, the design of means for catalyst regeneration and recycle is necessary for an effective coal liquefaction process. Several approaches to achieving these goals are discussed below. 

These additional yields point out the added benefits gained from the presence of additional donor hydrogen. The data in Figure 10 also show the sensitivity of increased yield from the bottoms recycle technique to the type of coal being processed. 

The attendent higher solvent recycle rate required for Wyoming coal will reduce the net benefit of bottoms recycle and will require critical comparison with the non-recycle case. 

Figure 10. Simulated bottoms recycle provides increased liquefaction liquid yields...

H. SIEGEL Also regarding the preparation of the feed slurry, you showed the bottom stream being recycled and mixed with the coal. Is there any other distillate stream completely free of solids that is also recycled to help form the feed slurry, or is it all bottoms recycle ... 

In the inner loop, the rate and composition of fractionator bottoms recycle are determined by successive substitution sometimes accelerated by a secant method. The rate and composition of recycle plus makeup gas routed to the reactor inlets and... 

Figure 2. Comparison on n-alkane distribution from Beulah lignite, A, and n-alkane distribution from CPU bottoms recycle product, (Beulah lignite feed coal).

Liquid wastes are generated in the decontamination of the WCF during down times for maintenance. The PEW wastes are evaporated, the bottoms recycled, and overhead further cleaned in an ion exchange column. The final eflBiuent is discharged to the service well at 50,000 gal/yr of low-level liquid waste as condensate. These wastes are also discharged to the service waste system without significant effect on the environment. 

The EDS process suggested that coal could be adequately hydrogenated in the absence of added catalyst. However, a later modification used vacuum bottoms recycle, in addition to the normal distillate solvent recycle, and displayed improved operating characteristics and higher distillate yield, particularly for low-rank coals. The increased residence time... 

In the first class, azeotropic distillation, the extraneous mass-separating agent is relatively volatile and is known as an entrainer. This entrainer forms either a low-boiling binary azeotrope with one of the keys or, more often, a ternary azeotrope containing both keys. The latter kind of operation is feasible only if condensation of the overhead vapor results in two liquid phases, one of which contains the bulk of one of the key components and the other contains the bulk of the entrainer. A t3q)ical scheme is shown in Fig. 3.10. The mixture (A -I- B) is fed to the column, and relatively pure A is taken from the column bottoms. A ternary azeotrope distilled overhead is condensed and separated into two liquid layers in the decanter. One layer contains a mixture of A -I- entrainer which is returned as reflux. The other layer contains relatively pure B. If the B layer contains a significant amount of entrainer, then this layer may need to be fed to an additional column to separate and recycle the entrainer and produce pure B. 

Wastewater leaves the process from the bottom of the second column and the decanter of the azeotropic distillation column. Although both these streams are essentially pure water, they will nevertheless contain small quantities of organics and must be treated before final discharge. This treatment can be avoided altogether by recycling the wastewater to the reactor inlet to substitute part of the freshwater feed (see Fig. 10.36). 

The urea produced is normally either prilled or granulated. In some countries there is a market for Hquid urea—ammonium nitrate solutions (32% N). In this case, a partial-recycle stripping process is the best and cheapest system. The unconverted NH coming from the stripped urea solution and the reactor off-gas is neutralized with nitric acid. The ammonium nitrate solution formed and the urea solution from the stripper bottom are mixed, resulting in a 32—35 wt % solution. This system drastically reduces investment costs as evaporation, finishing (priQ or granulation), and wastewater treatment are not required. 

A schematic of the MGCC process is shown in Figure 9. The mixed Cg aromatic feed is sent to an extractor (unit A) where it is in contact with HF—BF and hexane. The MX—HF—BF complex is sent to the decomposer (unit B) or the isomerization section (unit D). In the decomposer, BF is stripped and taken overhead from a condensor—separator (unit C), whereas HF in hexane is recycled from the bottom of C. Recovered MX is sent to column E for further purification. The remaining Cg aromatic compounds and hexane are sent to raffinate column E where residual BE and HE are separated, as well as hexane for recycle. Higher boiling materials are rejected in column H, and EB and OX are recovered in columns I and J. The overhead from J is fed to unit K for PX separation. The raffinate or mother Hquor is then recycled for isomerization. 

In the first step cumene is oxidized to cumene hydroperoxide with atmospheric air or air enriched with oxygen ia one or a series of oxidizers. The temperature is generally between 80 and 130°C and pressure and promoters, such as sodium hydroxide, may be used (17). A typical process iavolves the use of three or four oxidation reactors ia series. Feed to the first reactor is fresh cumene and cumene recycled from the concentrator and other reactors. Each reactor is partitioned. At the bottom there may be a layer of fresh 2—3% sodium hydroxide if a promoter (stabilizer) is used. Cumene enters the side of the reactor, overflows the partition to the other side, and then goes on to the next reactor. The air (oxygen) is bubbled ia at the bottom and leaves at the top of each reactor. 

The mixture is cooled and noncondensable gases are scmbbed with water. Some of the resultant gas stream, mainly hydrogen, may be recycled to control catalyst fouhng. The Hquids are fractionally distilled, taking acetone overhead and a mixture of isopropyl alcohol and water as bottoms. A caustic treatment maybe used to remove minor aldehyde contaminants prior to this distillation (29). In another fractionating column, the aqueous isopropyl alcohol is concentrated to about 88% for recycle to the reactor. 

The extract is vacuum-distilled ia the solvent recovery column, which is operated at low bottom temperatures to minimise the formation of polymer and dimer and is designed to provide acryUc acid-free overheads for recycle as the extraction solvent. A small aqueous phase in the overheads is mixed with the raffinate from the extraction step. This aqueous material is stripped before disposal both to recover extraction solvent values and minimise waste organic disposal loads. 

The bottoms from the solvent recovery (or a2eotropic dehydration column) are fed to the foremns column where acetic acid, some acryflc acid, and final traces of water are removed overhead. The overhead mixture is sent to an acetic acid purification column where a technical grade of acetic acid suitable for ester manufacture is recovered as a by-product. The bottoms from the acetic acid recovery column are recycled to the reflux to the foremns column. The bottoms from the foremns column are fed to the product column where the glacial acryflc acid of commerce is taken overhead. Bottoms from the product column are stripped to recover acryflc acid values and the high boilers are burned. The principal losses of acryflc acid in this process are to the aqueous raffinate and to the aqueous layer from the dehydration column and to dimeri2ation of acryflc acid to 3-acryloxypropionic acid. If necessary, the product column bottoms stripper may include provision for a short-contact-time cracker to crack this dimer back to acryflc acid (60). 

The wet ester is distilled in the dehydration column using high reflux to remove a water phase overhead. The dried bottoms are distilled in the product column to provide high purity acrylate. The bottoms from the product column are stripped to recover values and the final residue incinerated. Alternatively, the bottoms maybe recycled to the ester reactor or to the bleed stripper. 

The aqueous layer from the ester column distillate, the raffinate from washing the ester, and the aqueous phase from the dehydration step are combined and distilled in the alcohol stripper. The wet alcohol distillate containing a low level of acrylate is recycled to the esterification reactor. The aqueous column bottoms are incinerated or sent to biological treatment. Biological treatment is common. 

A schematic diagram of a six-vessel UOP Cyclesorb process is shown in Figure 15. The UOP Cyclesorb process has four external streams feed and desorbent enter the process, and extract and raffinate leave the process. In addition, the process has four internal recycles dilute raffinate, impure raffinate, impure extract, and dilute extract. Feed and desorbent are fed to the top of each column, and the extract and raffinate are withdrawn from the bottom of each column in a predeterrnined sequence estabUshed by a switching device, the UOP rotary valve. The flow of the internal recycle streams is from the bottom of a column to the top of the same column in the case of dilute extract and impure raffinate and to the top of the next column in the case of dilute raffinate and impure extract. 

---