Sulfur operation

Title 30, Oil and Gas and Sulfur Operations in the Outer Part 250 Continental Shelf... 

Fischer A process for removing hydrogen sulfide from coal gas by absorption in an aqueous solution of potassium ferrocyanide and bicarbonate the solution is regenerated electro-chemically with the production of elemental sulfur. Operated at the Hamburg gasworks in the 1930s. 

The mechanisms by which the solid, insoluble mineral sulfides are biologically oxidized have been less intensively studied and the details of the interactions are incompletely understood. As will be discussed in greater detail in later sections, not only are mechanisms facilitating the oxidation of sulfur operative but an important role is played by iron oxidation reactions. The reactions of greatest significance in the biological oxidation of sulfide minerals are summarized in Table 6.3.3. 

Sulfur compounds (H2S, SO2, organic sulfur) Operating tern perature up to 400°C Measurement range 0.05-0.5 ppm Response time <1 min at 0.05 ppm Gas environment Hydrogen, CO, CO2, hydrocarbons, water vapor... 

Case 1 Hydrotreater producing 500 wppm sulfur operating at 32 bar hydrogen pressure on a low sulfur, straight-run feedstock. 

This case is based on straight-run low sulfur gas oil containing 0.2 wt% sulfur operating at a hydrogen partial pressure at the inlet of 32 bar. Feedstock properties are given in Table 4. The catalyst is TK-574, a high activity CoMo catalyst. Catalyst cycle length is fixed at l / years. 

San Cristobal to Mexican Gulf Sulfur Jaltipan to Pan-American and Salinas to Gulf Sulfur (Azufre Vera Cruz). The only Mexican Frasch company that did not originate from the exploration of the Brady Brothers was CEDI, the Texas Gulf Sulfur operations. The adventures of these Mexican sulfur explorers were presented in a Time Magazine article on February 21, 1955. 

BOEMRE rules are collected in the Federal Register under 30 CFR (Code of Federal Regulations) Part 250. The title of this code is OH and Gas and Sulfur Operations in the Outer Continental Shelf. It covers exploration, development, and production. Part (b)(2) of Section 250.101 summarizes its overall intent ... 

Using a batch reactor, a constant concentration of sulfuric acid can be maintained by adding concentrated sulfuric acid as the reaction progresses, i.e., semi-batch operation. Good temperature control of such systems can be maintained, as we shall discuss later. 

The main justification for diesel fuel desulfurization is related to particulate emissions which are subject to very strict rules. Part of the sulfur is transformed first into SO3, then into hydrated sulfuric acid on the filter designed to collect the particulates. Figure 5.21 gives an estimate of the variation of the particulate weights as a function of sulfur content of diesel fuel for heavy vehicles. The effect is greater when the test cycle contains more high temperature operating phases which favor the transformation of SO2 to SO3. This is particularly noticeable in the standard cycle used in Europe (ECE R49). 

Finally, sulfur has a negative effect on the performance of the catalyst itself. One sees for example in Figure 5.23 that the initiation temperature increases with the sulfur level in the diesel fuel, even between 0.01% and 0.05%. Yet, in the diesel engine, characterized by relatively low exhaust temperatures, the operation of the catalyst is a determining factor. One can thus predict an ultimate diesel fuel desulfurization to levels lower than 0.05%. 

H2S is found with the reservoir gas and dissolved in the crude (< 50 ppm by weight), but it is formed during refining operations such as catalytic cracking, hydrodesulfurization, and thermal cracking or by thermal decomposition of sulfur[Pg.322]

Of the general formula, R - S — H, where R represents an aliphatic or cyclic radical, the thiols —also known as mercaptans— are acidic in behavior owing to their S—H functional group they are corrosive and malodorous. Their concentration in crude oils is very low if not zero, but they are created from other sulfur compounds during refining operations and show up in the light cuts, as illustrated in Table 8.6. 

Mercaptans are naturally present in crude oil (Chapters 1 and 8), or they result from the decomposition of other sulfur compounds during thermai or catalytic cracking operations. 

Alkylation of 2-methylaminothiazole (204) with ROH in 85% sulfuric acid gives 2-methylimino-3-alkyl-4-thiazoIine (54). 2-Amino-4-rnethyl-thiazoie alkylated with an excess of isopropanol, however, gives 95% of 2-isopropylamino-4-methyl-5-isopropylthiazole (56). The same result is obtained with cyclohexanol (242). These results and those reported in Sections III.l.C and IV.l.E offer interesting new synthetic possibilities in thiazole chemistry. The reactive species in these alkylations is the conjugate acid of 2-aminothiazole. and the diversity of the products obtained suggests that three nucleophilic centers may be operative in this species. 

Small amounts of propionitrile and bis(cyanoethyl) ether are formed as by-products. The hydrogen ions are formed from water at the anode and pass to the cathode through a membrane. The catholyte that is continuously recirculated in the cell consists of a mixture of acrylonitrile, water, and a tetraalkylammonium salt the anolyte is recirculated aqueous sulfuric acid. A quantity of catholyte is continuously removed for recovery of adiponitrile and unreacted acrylonitrile the latter is fed back to the catholyte with fresh acrylonitrile. Oxygen that is produced at the anodes is vented and water is added to the circulating anolyte to replace the water that is lost through electrolysis. The operating temperature of the cell is ca 50—60°C. Current densities are 0.25-1.5 A/cm (see Electrochemical processing). 

Acryflc acid, alcohol, and the catalyst, eg, sulfuric acid, together with the recycle streams are fed to the glass-lined ester reactor fitted with an external reboiler and a distillation column. Acrylate ester, excess alcohol, and water of esterification are taken overhead from the distillation column. The process is operated to give only traces of acryflc acid in the distillate. The bulk of the organic distillate is sent to the wash column for removal of alcohol and acryflc acid a portion is returned to the top of the distillation column. If required, some base may be added during the washing operation to remove traces of acryflc acid. 

A continuous bleed is taken from the reactor to remove high boilers. Values contained in this bleed are recovered in the bleed stripper and the distillate from this operation is recycled to the esterification reactor. The bleed stripper residue is a mixture of high boiling organic material and sulfuric acid, which is recovered for recycle in a waste sulfuric acid plant. 

The sulfuric acid hydrolysis may be performed as a batch or continuous operation. Acrylonitrile is converted to acrylamide sulfate by treatment with a small excess of 85% sulfuric acid at 80—100°C. A hold-time of about 1 h provides complete conversion of the acrylonitrile. The reaction mixture may be hydrolyzed and the aqueous acryhc acid recovered by extraction and purified as described under the propylene oxidation process prior to esterification. Alternatively, after reaction with excess alcohol, a mixture of acryhc ester and alcohol is distilled and excess alcohol is recovered by aqueous extractive distillation. The ester in both cases is purified by distillation. 

Steps such as the substitution of low sulfur fuels or nonvolatile solvents, change of taw materials, lowering of operation temperatures to reduce NO formation or vo1ati1i2ation of process material, and instaHion of weU-designed hoods (31—37) at emission points to effectively reduce the air quantity needed for pollutant capture are illustrations of the above principles. 

In the commonly used Welland process, calcium cyanamide, made from calcium carbonate, is converted to cyanamide by reaction with carbon dioxide and water. Dicyandiamide is fused with ammonium nitrate to form guanidine nitrate. Dehydration with 96% sulfuric acid gives nitroguanidine which is precipitated by dilution. In the aqueous fusion process, calcium cyanamide is fused with ammonium nitrate ia the presence of some water. The calcium nitrate produced is removed by precipitation with ammonium carbonate or carbon dioxide. The filtrate contains the guanidine nitrate that is recovered by vacuum evaporation and converted to nitroguanidine. Both operations can be mn on a continuous basis (see Cyanamides). In the Marquerol and Loriette process, nitroguanidine is obtained directly ia about 90% yield from dicyandiamide by reaction with sulfuric acid to form guanidine sulfate followed by direct nitration with nitric acid (169—172). 

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