GB2032404A

GB2032404A - Regeneration of Zinc Chloride Catalyst

Info

Publication number: GB2032404A
Application number: GB7841974A
Authority: GB
Original assignee: Conoco Inc
Current assignee: ConocoPhillips Co
Priority date: 1978-10-26
Filing date: 1978-10-26
Publication date: 1980-05-08
Also published as: GB2032404B

Abstract

Improved rate of recovery of zinc values from the solids which are carried over by the effluent vapors from the oxidative vapor phase regeneration of spent zinc chloride catalyst is achieved by treatment of the solids with both hydrogen chloride and calcium chloride to selectively and rapidly recover the zinc values as zinc chloride. The process is particularly applicable to the regeneration of molten zinc chloride catalysts used in the hydrocracking of coaly solids and products derived from coaly solids.

Description

SPECIFICATION Regeneration of Zinc Chloride Catalyst This invention relates to the regeneration of spent zinc chloride catalyst. It is particularly applicable to the regeneration of molten zinc chloride catalyst used in the hydrocracking of coaly solids and products derived from coaly solids such as coal extracts or coal liquefaction products, but our invention is also applicable to the regeneration of other zinc chloride catalysts whose contaminants can be removed by the process of our invention.

A process for utilizing molten zinc chloride in such catalytic hydrocracking is described in British Patent No. 1,095,851. As set forth in that patent, it was found that polynuclear hydrocarbons, even those which are nondistillable, may be readily converted in the presence of a large quantity of molten zinc chloride to low boiling liquids suitable for fuels, such as gasoline. The amount of zinc chloride which serves as catalyst is at least 1 5 weight percent of the inventory of hydrocarbonaceous material in the hydrocracking zone.To this amount of zinc chloride is added, in the case of nitrogen- and sulfur-containing feedstock, sufficient zinc chloride to remove reactive nitrogen and sulfur compounds in the feedstock, in accordance with the following equations: (1) ZnCl2+H2S=ZnS+HCl (2) ZnCI2+NH3=ZnCI2 NH3 (3) ZnCl2. NH3+HCI=ZnCI2. NH4Cl In the case of a feedstock consisting of coal extract containing, for example, 1.5 percent N and 2 percent S, the amount of zinc chloride required to react stoichiometrically with the nitrogen and sulfur compounds would be 23 percent by weight of the feedstock.

The spent zinc chloride melt from the hydrocracking zone contains (in addition to zinc chloride) zinc sulfide (see Equation 1), ZnCl2. NH3 (see Equation 2), organic residue, and ash, as well as zinc oxide if the latter were used as an HCI acceptor. U.S. Patent 3,355,376 described two methods of regenerating the spent zinc chloride melt, both involving oxidation of the impurities, one in liquid phase and one in vapor phase.The reactions occurring in such oxidative regenerative processes are set forth in the following equations: (4) NH3+3/4 02=1/2 N2+3/2 H2O (5) ZnO+2 HCi=ZnCI2+H2O (6) ZnS+3/2 O2=ZnO+SO2 (7) C+O2=CO2 (8) C+1/2O2=CO In vapor phase oxidation, air is used to effect combustion of the organic residue, to thereby establish and maintain a temperature in the regenerator at which zinc chloride is vaporized.

The effluent zinc chloride vapors carry with them finely divided solids containing zinc values in the form of water-soluble and water-insoluble compounds, for example, "free" zinc oxide and zinc oxide chemically combined with acidic oxides such as silica which are present in the feedstocks to the hydro-cracking zone.

In our U.S. Patent Number 4,081,400, a process is described for recovery of zinc values which are entrained in the effluent zinc chloride vapors from a vapor phase oxidative regenerator.

The regenerative process therein described comprises four steps. In the first step, the spent zinc chloride melt from the hydrocracking zone is subjected to vapor phase oxidative treatment by combustion of the carbon and sulfur compounds, as well as any ammonia that may be present. In this step, the temperature is maintained at least high enough to assure vaporization of the zinc chloride. The effluent vapors contain finely divided solids composed of zinc oxide and zinc oxide complexes derived from the feedstock to the hydrocracking zone, some of which we now know to be water-soluble, and some water-insoluble, e.g. ZnO . SiO2. There generally is some residual organic residue in the entrained solids. The second step of the process consists of the separation of the zinc chloride vapors from the solids by any conventional means, generally a cyclone.The third step consists of the treatment of the separated solids with a hydrogen chloridecontaining gas under conditions favoring the reaction of zinc oxide and hydrogen chloride at a temperature sufficiently high to form zinc chloride in the vapor state. In the fourth step, vaporous zinc chloride is separated from the ash and condensed to the molten state for recycle to the hydro-cracking zone.

The primary object of the present inMention is to provide an improvement in the process for regenerating spent zinc chloride whereby the rate of recovery of zinc values from the solids entrained in the effluent zinc chloride vapors from the regenerator is increased.

The following patents were considered in the preparation of this specification: Br. Patent 1,095,851 U.S. Patent 3,355,376 U.S. Patent 3,371,049 U.S. Patent 3,594,329 U.S. Patent 3,625,861 U.S. Patent 3,629,159 The regeneration process of our invention is an improvement and modification of the abovedescribed four-step process. We have observed that the rate of recovery of water-insoluble zinc values from the separated solids from the second step of said process is relatively slow. Our invention consists in treating said separated solids with both hydrogen chloride and calcium chloride, whereby the rate of recovery of the water-insoluble zinc values is improved.This behaviour may be explained by the following equation: ZnO . SiO2+CaCI2=CaO SiO2+ZnCI2t Thus one aspect of our invention provides a process for regenerating a spent zinc chloride catalyst which contains zinc chloride, watersoluble and water-insoluble zinc values in solid form, and carbonaceous residue, said process comprising: (a) subjecting said spent catalyst to vapor phase oxidative treatment whereby effluent zinc chloride vapors are produced which contain water-soluble and water-insoluble zinc values in solid form; (b) separating the zinc chloride vapors from said solids; (c) subjecting said separated solids to contact with both calcium chloride and with hydrogen chloride-containing gas under reaction conditions whereby the zinc values react therewith to form zinc chloride; and (d) recovering said zinc chloride in a substantially solids-free molten state.

The accompanying drawing is a schematic flowsheet of a preferred embodiment of the improved regeneration process of the present invention.

Referring to the drawing, spent zinc chloride melt is fed to a Combustor 10 through a conduit 1 2. The spent zinc chloride melt resulting from the hydrocracking of coal or coal derived products contains, in addition to zinc chloride, carbonaceous residue as well as ash, sulfur, and nitrogen components. The carbon, sulfur and nitrogen components in the spent catalyst are oxidized by air fed to the Combustor via a conduit 14. The air preferably contains a low concentration of HCI to aid in preventing hydrolysis of zinc chloride by steam. The combustion conducted in the Combustor may be either with less than or greater than, the stoichiometric amount of air. In the former case, fuel gas will be produced; in the latter case, flue gas.

Heat is generated in the Combustor by oxidation of the carbon contained in the spent melt, and is sufficient to maintain the temperature in the Combustor above the vaporization temperature of zinc chloride. The latter, in vapor form, together with steam, non-condensable gases, N2, CO and CO2, unreacted HCI, and entrained solids, is withdrawn from the Combustor 10 through a conduit 1 6 to a hot Separator 18 which is any cyclone commonly used for the separation of gases and solids at high temperature. In this instance, the temperature of the cyclone is not permitted to drop below the condensation point of zinc chloride.

Zinc chloride and water vapors and noncondensable gases CO, CO2, N2 and HCI are withdrawn from the Separator 1 8 through a conduit 20 to a condenser 22 for selective condensation after passing through a pre-cooler 21. Zinc chloride condensate in molten form is discharged from the condenser 22 through a conduit 24 for return to the hydrocracking zone (not shown). The non-condensable gases are withdrawn from the condenser through conduit 26 to a suitable HCI recovery zone 28 from which HCI is recovered through conduit 30 for reuse in the process. A gas is withdrawn from the HCI recovery zone through conduit 32 which is a low sulfur fuel gas whenever sub-stoichiometric quantities of air are used in Combustor 10.

A typical analysis of the separated solids from Separator 18 is as follows: Table I Analysis of Cyclone Ash (% by weight) Zn (in the form of water soluble zinc compounds) 2.94 Zn (in the form of water insoluble zinc compounds) 4.54 Cl 4.92 H 0.08 C 0.09 S 0.37 Na20 0.10 K20 0.03 CaO 11.40 MgO 4.45 Fe203 3.90 TiO2 0.94 SiO2 42.86 AI2O3 18.41 95.03* *Other compounds were obviously present that could not be readily determined.

The solids discharged from the hot Separator 18 are conducted by a conduit 34 to a premixer and preheater 35. CaCI2 in finely divided form is introduced into conduit 34 from a hopper 36. The amount is preferably twice the amount needed to react with the water-insoluble zinc compounds, as determined by analysis. The solids are mixed with a stream of HCI-containing gas introduced through a conduit 38. The gas may conveniently be air or combustion gases. The mixture of gases and entrained solids is transferred to a second Combustor 40 where the zinc oxide and zinc oxide complexes are converted to zinc chloride by reaction with HCI and CaCI2. The temperature of the Combustor is maintained above the vaporization temperature of zince chloride, for example 17000 F, by the oxidation of carbon in the case where oxygen is contained in the HCI containing gas. The carbon is that contained in the unconsumed organic residue carried over from the first Combustor or is added as required to the second Combustor expressly for that purpose. Such added or supplemental carbon may be in the form of coal.

Zinc chloride vapors, ash and non-condensable gases are withdrawn from the Combustor 40 through a conduit 42 to a hot cyclone Separator 44 where the ash containing added calcium is rejected through a line 46. The vapors and gases pass through a pre-cooler 48 in a conduit 50 to a condenser 52 adapted to selectively condense zinc chloride in molten form. The molten zinc chloride is withdrawn through line 54 for recycle.

The non-condensable gas is withdrawn through a conduit 56 to a suitable HCI recovery zone 58 for recovery of HCI through a conduit 60. The HCI-free gas, together with any sulfur-rich gas withdrawn from conduit 32 through a conduit 61, is conducted through a conduit 62 to an SO2- reduction zone 64 for conversion of SO2 in the gas to elemental sulfur. The amount of SO2 in conduit 32 and in conduit 62 is a function of the amount of air used in Combustor 10, the larger the amount of air, the greater the amount of SO2 in conduit 32, and conversely the smaller the amount, the larger the amount in conduit 62. In either case, it is desirable to recover such SO2 as sulfur. The CO and H2 contained in the gas provides a suitable source of reducing agent for SO2 reduction. The sulfur product is recovered through a conduit 66. The remaining gas may be, incinerated in an incinerator 67 to remove residual sulfur compounds.

In the foregoing specification, the principle, preferred construction and mode of operation of the invention have been explained and what is considered to represent its best embodiment has been illustrated and described. However, it should be understood that, within the scope of the appended claims, the invention may be practised otherwise than as specifically illustrated and described.

Claims

1. A process for regenerating a spent zinc chloride catalyst which contains zinc chloride, water-soluble and water-insoluble zinc values in solid form, and carbonaceous residue, said process comprising: (a) subjecting said spent catalyst to vapor phase oxidative treatment whereby effluent zinc chloride vapors are produced which contain water-soluble and water-insoluble zinc values in solid form; (b) separating the zinc chloride vapors from said solids; (c) subjecting said separated solids to contact with both calcium chloride and with hydrogen chloride-containing gas under reaction conditions whereby the zinc values react therewith to form zinc chloride; and (d) recovering said zinc chloride in a substantially solids-free molten state.

2. A process according to claim 1 wherein said spent zinc chloride catalyst has been used as a molten catalyst to catalyze the hydrocracking of coaly solids or products derived therefrom.

3. A process according to claim 1 or 2 wherein said vapor phase oxidative treatment is performed in a combustor, heat generated by oxidation of carbon in said spent catalyst being sufficient to maintain the temperature in the combustor above the vaporization temperature of zinc chloride.

4. A process according to any of the preceding claims wherein there is used about twice the amount of calcium chloride needed to react with said water-insoluble zinc values.

5. A process accordng to any of the preceding claims wherein said step (c) is-performed in a combustor maintained above the vaporization temperature of zinc chloride.

6. A process according to claim 1, substantially as described herein.

7. A process for regenerating a spent zinc chloride catalyst, substantially as illustrated in the accompanying drawing.

8. A process for hydrocracking coaly solids or products derived therefrom in the presence of a molten zinc chloride catalyst, wherein spent catalyst is regenerated by the process of any of claims 1-7.