US3817725A

US3817725A - Gasification of solid waste material to obtain high btu product gas

Info

Publication number: US3817725A
Application number: US00252450A
Authority: US
Inventors: R Sieg; R White
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1972-05-11
Filing date: 1972-05-11
Publication date: 1974-06-18
Anticipated expiration: 1991-06-18

Abstract

(D) WITHDRAWING NET PRODUCT COMBUSTIBLE GASES FROM THE GASIFICATION ZONE OR FROM THE METHANATION ZONE.

A PROCESS FOR CONVERTING SOLID WASTE MATERIAL TO COMBUSTIBLE GASES WHICH COMPRISES: (A) HEATING AND REACTING THE WASTE MATERIAL WITH REACTIVE GASES IN A GASIFICATION ZONE TO OBTAIN SAID COMBUSTIBLE GASES AND WITHDRAWING THE COMBUSTIBLE GASES FROM THE GASIFICATION ZONE, (B) METHANATING AT LEAST A PORTION OF SAID COMBUSTIBLE GASES IN A METHANATION ZONE TO OBTAIN METHANATED GASES, (C) FEEDING AT LEAST A PORTION OF SAID METHANATED GASES TO THE GASIFICATION ZONE, AND

Description

June 18, 1974 R. P. SIEG El'AL 3,812,725 GASIFICATION OF SOLID WASTE MATERIAL TO OBTAIN HIGH B.T.U. PRODUCT GAS Filed May 11, 1972 l5 MAKE-UP WATER A +nq2 CO3 OR K2 CO3 PRODUCT HIGH BTU GAS m COMPRESSOR 7 RECYCLE GAS Cb WASTE) 4 7 GASIFIER i A SOLID WASTES QUENCH DRUM ' I RECOVERED .r PRODUCT 9 OIL HIGH BTU GAS SETTLER 33 ASH RECYCLE HEAT COMBUSTOR 2o RECOVERY 1 v A AIR 3/ 29 METHANATION Smtes Patent Ofice 3,817,725 Patented June 18, 1974 3,817,725 GASIFICATION F SOLID WASTE MATERIAL TO OBTAIN HIGH B.T.U. PRODUCT GAS Robert P. Sieg, Piedmont, and Robert J. White, Pinole,

Califi, assignors to Chevron Research Company, San

Francisco, Calif.

Filed May 11, 1972, Ser. No. 252,450 Int. Cl. C103 3/00, 3/16 U.S. Cl. 48-209 8 Claims ABSTRACT OF THE DISCLOSURE RELATED APPLICATIONS The commonly-assigned application of John R. B. Ellis and Frederick C. Franklin titled Gasification of Solid Carbonaceous Waste Material, filed concurrently with the present application, is related to this application.

BACKGROUND OF THE INVENTION The present invention relates to gasification of solid material.

Previous gasification methods for solids mostly fall into the classifications of eduction processes or partial oxidation processes.

Eduction type processes are described in U.S. Pat. No. 1,055,334, Process of Making Gas; U.S. Pat. No. 2,640,- 014, Oil-Shale Eduction Process and Apparatus; and U.S. Pat. No. 3,361,644, Shale Retorting Process.

According to the U.S. Pat. No. 1,055,334, process gas is obtained from coal by distillation comprising passing the gas-making material between heated walls in a finely divided condition and while separated and distributed in a substantially non-oxidizing medium and distilling the material during such passage and regulating the motion of the material and said medium by imparting thereto a vortical motion by jets of heated gas directed along the heated walls transversely to the direction of passage.

It can be noted, however, that coal distillation is not gasification. Distillation drives ofl? volatile matter already present; gasification creates volatiles not originally present.

In the process of U.S. Pat. 2,640,014, part of the material left after eduction of oil from the shale feed is burned to ashes with the resulting hot gas then being used to educt gas and oil from the shale feed material.

According to U.S. Pat. 3,361,644, gases and oil are educted from shale by passing oxygen-free hot gas countercurrent to downflowing shale particles. The hot gas is obtained by heating a portion of the gas eflluent from the eduction zone. Temperature is maintained below about 1800 F. in the eduction zone to avoid clinker formation by fusion of ash constituents. The process of U.S. Pat. 3,361,644 is largely a pyrolysis-distillation process which is not based on a gasification reaction such as reacting H O with carbonaceous material.

Partial oxidation processes are described, for example, in U.S. Pat. Nos. 1,977,684; 2,592,377; 2,657,986; 2,633,- 417; 2,727,812; 2,987,387; 2,657,124; and 3,025,149.

These processes all involve injection of oxygen into the reaction zone. Also, steam is usually injected into the reaction zone.

U.S. Pat. No. 2,660,521 is directed to partial oxidation of gases with expansion of the resultant hot gases through a turbine and thereby generating power and obtaining a cooled synthesis gas. Temperature in the reaction zone is controlled by carbon dioxide recycle. The carbon dioxide is a diluent and also lowers temperature by virtue of the endothermic reaction of carbon dioxide with hydrocarbon to form carbon monoxide and hydrogen.

Production of hydrogen and other combustible gases from waste substances produced in the manufacture of paper from wood chips and the like has been discussed in the literature, as, for example, in U.S. Pat. 3,317,292. In the manufacture of paper, wood chips are digested, for example, with an aqueous calcium sulfide liquid thereby forming calcium lignin sulfonate Waste product in solution, leaving wood pulp behind. As disclosed in U.S. Pat. 3,317,292, the waste substances containing ligninderived organic components can be converted to a gas mixture comprising hydrogen by contacting the waste material with steam in a reaction zone at an elevated temperature at least of the order of several hundred degrees centigrade.

Both US. Pat. 1,777,449, titled Process of Producing Gas From Garbage, and U.S. Pat. 3,471,275, titled Method of Disposal of Refuse, are directed to producing combustible gases in an externally heated retort rather than by introducing hot gases directly into the retort vessel.

SUMMARY According to the present invention a process is provided for converting solid waste material to combustible gases which comprises:

(a) Heating and reacting the Waste material with reactive gases in a gasification zone to obtain said combustible gases and withdrawing the combustible gases from the gasification zone,

(b) Methanating at least a portion of said combustible gases in a methanation zone to obtain methanated gases,

(c) Feeding a portion of said methanated gases to the gasification zone, and

(d) Withdrawing net product combustible gases from the gasification zone or from the methanation zone.

The present invention, among other features, is based on the combination of waste solids gasification with the methanation and recycling of a portion of the combustible gas efliuent from the gasification zone. Also, temperature control in the gasification zone is preferably obtained by partially or wholly burning a second portion of the effluent gases from the gasification zone and then recycling the hot gases thus obtained to the gasification zone. It is critical in the process of the present invention that gasification reactions are carried out in the gasification zone to generate hydrogen and carbon oxides from hydrocarbonaceous matter in the gasification zone and also to generate hydrogen from the H 0 which is added to the reaction zone via the recycled hot gases. The present invention is also based on a critically important third feature or concept which is that the present process is extremely attractive for the conversion of solid wastes to high B.t.u. gas.

The term high B.t.u. gas is used herein to mean gas having a B.t.u. value of at least B.t.u. per cubic foot and preferably above 300 B.t.u. per cubic foot. With CO removal from the product gas of the present invention the B.t.u. content would be closer to 300 B.t.u./ft. and with both CO removal from the product gas and use of purified oxygen (instead of air) for the burning of said recycled second portion, the B.t.u. content would be about 400-800 B.t.u./ftfi.

The term solid waste material is used herein to connote municipal garbage, industrial or agricultural wastes which are organic, such as cellulosic solids, dried or partially dried sewage, and such as cellulosic solids, dried or partially dried sewage, and like solid waste materials.

The term methanation is used herein to mean conversion of carbon oxides and H to methane by reaction of the carbon oxides with H For example:

The methanation reaction is exothermic, and this exothermic heat of reaction is integrated into the process of the present invention to supply a portion of the heat required for the endothermic reactions in the gasification zone. In the process of the present invention the temperatures in the gasification zone are highly advantageously controlled by means of adjusting the temperature and/or amount of methanated gases recycled to the gasification zone and preferably also by means of adjusting external to the gasification zone the temperature and/or amount of a second hot recycle gas stream to the gasification zone.

Thus, the temperatures in the gasification zone can be controlled pursuant to the present invention by controlling both the amount of each hot recycle gas stream and the temperature of each recycle gas. Usually all four of these variables will be adjusted to an optimum level for the process of the present invention so as to achieve desired reaction rates of solids in the gasification zone at minimum energy requirement for recycle gas compression, but yet to maintain temperatures in the gasification zone below about 2000 F.

One of the particular advantages of the present invention is that the recycle of methanated gases allows an added means for temperature control in the gasification zone. Usually the main means of heat input and temperature control in the gasification zone is by the second hot recycle gas stream.

In the process of the present invention, the advantageous services which are afiorded by the integrated methanation step include the following:

(1) Increase B.t.u. of product gas by raising CH content of product gas.

(2) Provide heat input source for gasification reaction.

(3) Provide temperature control for gasification reaction.

To reduce the amount of reversal of the methanation reaction when the recycled methanated gases are introduced to the gasification reactor, it is preferable to introduce the methanated gases to about the middle of the reactor where the temperature is about 800-1200 F. versus about 1600-2000 F. at the bottom and ZOO-600 F. at the top. Thus, according to a preferred embodiment of the present invention wherein the gasification zone comprises an upright cylindrical gasifier reactor, the methanated gases are introduced at a central position along the length of said gasifier, feed waste material is introduced at an upper position along the length of said gasifier and heating gases are introduced at a lower position along the length of said gasifier.

The gases obtained from the gasification zone are preferably cooled and cleansed by a water quench. This water in part finds its way back to the gasification zone via that portion of the gases which are recycled to supply heat and reactive gases to the gasification zone. Additional water is supplied to the gasification zone from the solids fed to the gasification zone, as the solids fed invariably will have at least some moisture content. Additional water and carbon dioxide are produced by partial burning of the recycle gas. Thus, there will be H and CO present in the gasification zone for conversion of carbon and hydrocarbons into hydrogen and carbon monoxide according to well known reactions such as 4 BRIEF DESCRIPTION OF THE DRAWING The drawing is a schematic process flow diagram illustrating a preferred embodiment of the present invention.

DETAILED DESCRIPTION OF THE DRAWING Referring more particularly to the drawing, solid wastes are introduced via line 1 to gasification zone 2. The solid wastes can be chosen from a variety of feeds such as municipal garbage (paper, orange peels, grease, bones, plastics, etc.); agricultural wastes (corn stalks, etc.); sewage, preferably in dried form; and the like. Other solid feeds, e.g. carbonaceous f'eeds such as coal, peat, lignite or the like, can be fed to the process of the present invention, but a critical concept for the preferred embodiment of the present invention is the use of the process of present invention to convert solid waste material to high B.t.u. gas.

The solids can be considered to undergo a series of steps or reactions in the gasification zone including, for example, H O distillation, oil distillation, pyrolysis, and gasification reactions such as previously mentioned. In the present invention there must be gasification reactions in the gasification zone.

Ashes are withdrawn from the bottom of the gasification zone as indicated via line 3.

A gaseous stream is withdrawn from the gasification zone as indicated by line 4. This gas stream is quenched and scrubbed to remove particles by water introduced to quench drum 6 via line 7 and recycle line 8. Makeup water and preferably an alkali carbonate catalyst is introduced via line 5. The water serves to quench the gasifier effluent, and the hot gasifier efiiuent gases serve to heat water for efiicient subsequent use in the gasifier. The heated water is ultimately recycled via lines 9 and 10 to gasifier 2.

The water preferably carries alkali carbonate catalyst to the gasifier to catalyze the reaction of solid waste material in gasifier 2 as is further described in the commonly assigned application of R. J. White, titled Catalytic Hydrogen Manufacture, filed May 5, 1970, Ser. No. 34,844.

Heavy sludge material and water is withdrawn from quench drum 6 via line 9 and passed to settler 11 via line 9. Oily sludge material, water, and preferably alkali catalyst is passed to gasifier 2 via line 10 from the settler. A clarified oil stream is withdrawn from an intermediate point from settler 11 via line 12.

The hot gases withdrawn from gasifier 2 via line 4 are introduced to the quench drum at a temperature of about 600 F., and the water scrub in the quench drum cools the gases to a temperature of 350 'F. before they are removed via line 13.

The gaseous material in line 13 is then split into two streams; a first stream 14 for recycle back to the gasification zone, and a second stream 15 which can be referred to as a product gas stream.

Preferably a portion of the recycle gases from quench drum 6 are passed to the recycle combustor via recycle compressor 22 and then line 23. Compressed air or pressurized oxygen is introduced to recycle combustor 24 via line 20. Recycle combustor 24 is preferably an in-line burner device. The partially combusted recycle gas is withdrawn from recycle combustor 24 usually at a temperature of about 2000 F. and passed via line 25 to the bottom of gasification zone 2 to supply reactive gases and temperature control as well as heat for gasification zone 2.

In the present invention it is critical to methanate a portion of the recycle gases. Thus recycle gas is passed via

lines

23 and 27 to methanation zone 28. In the methanation zone methane is formed by reacting carbon oxides with hydrogen. The carbon oxidesand hydrogen are present in the recycle gas due to gasification reactions in gasitier 2. Preferably the methanation reaction is carried out catalytically over a methanation catalyst. Such catalysts are known in the art and typically contain nickel.

If the methanation catalyst is sulfur sensitive, sulfur removal should be effected before the recycle gases are introduced to the methanator. Sulfur compounds can be removed by many known methods, such as by use of a bed of solid particles containing zinc oxide.

Usually the gases fed to the methanation zone will be preheated to about 500700 F and, due to the exothermic heat of the methanation reaction, the methanated gases leaves the methanator at about 650-1000 F. One of the advantageous features of the present invention is the utilization of this exothermic heat of reaction in the solid wastes gasification reaction zone. Thus the methanated gases are passed via

lines

29 and 31 to gasifier 2.

Previously product gas stream 15 was mentioned. Stream 15 can be the entire product stream, but advantageously a portion or all of the product gases are withdrawn, after methanation, from methanation zone 28 via

lines

29, 31 and 33. Gases withdrawn from the methanation step have a higher B.t.u. content than the gases in line 15, and thus the process of the present invention has the advantage of adjustable B.t.u. content for the product gas by, e.g., blending various portions of stream 15 with stream 33. The product high B.t.u. gas can be used as town gas in residential gas burning appliances or as a fuel gas for industrial furnaces.

Heat recovery zone 32 connotes recovery of heat from product gases withdraw from the methanation step; this heat recovery step is advantageously integrated into the process of the present invention as a heat input source for the feed gas to methanation zone 28.

Although various embodiments of the invention have been described, it is to be understood that they are meant to be illustrative only and not limiting. Certain features may be changed without departing from the spirit or scope of the present invention. It is apparent that the present invention has broad application to gasification of solid wastes with methanation of recycle gases to the gasification zone. Accordingly, the invention is not to be construed as limited to the specific embodiments discussed, but only as defined in the appended claims or substantial equivalents of the claims.

What is claimed is:

1. A process for converting solid Waste material to combustible gases which comprises:

(a) heating and reactingthe waste material with reactive gases in a gasification zone to obtain said combustible gases and withdrawing the combustible gases from the gasification zone,

(b) methanating at least a portion of said combustible bases in a methanation zone to obtain methanated gases, and

(c) feeding a portion of said methanated gases through the gasification zone thereby increasing the methane content and B.t.u. value of said combustible gases and transferring the sensible heat from said methanated gases to said gasification zone.

2. A process in accordance with claim 1 wherein the gasification zone comprises an upright cylindrical gasifier reactor vessel and the methanated gases are introduced at a central position along the length of said gasifier, feed waste material is introduced at an upper position along the length of said gasifier, and heating gases are introduced at a lower position along the length of said gasifier.

3. A process in accordance with claim 1, which comprises the further steps of (d) partially or wholly burning a portion of said combustible gases in a recycle gas combustion zone to obtain hot recycle gas containing essentially no oxygen, and

(e) passing the hot recycle into the gasification zone to supply heat and said reactive gases to the carbonaceous material.

4. A process in accordance with claim 3 wherein the temperature in the gasification zone is controlled to below about 2000 F. by means of adjusting the temperature of, or amount of, said hot recycle gas to the gasification zone.

5. A process for converting solid waste material to combustible gases, said process being free of carbon dioxide removal stages, which comprises:

I (a) heating and reacting the waste material with reactive gases in a gasification zone to obtain said combustible gases and withdrawing the combustible gases from the gasification zone,

(b) partially or wholly burning a portion of said withdrawn combustible gases in a recycle gas combustion zone to obtain hot recycle gas containing essentially no oxygen,

(c) passing the hot recycle gas into the gasification zone to supply heat and at least a portion of said reactive gases to the carbonaceous material,

(d) methanating at last a portion of said combustible gases in a methanation zone to obtain methanated gases, and

(e) feeding a portion of said methanated gases through the gasification zone thereby increasing the methane content and B.t.u. value of said combustible gases and transferringthe sensible heat from said methanation gases to said gasification zone.

6. A process in' accordance with claim 5 wherein the temperature in the gasification zone is controlled to below about 2000 F. by means of adjusting the temperature of or amount of said hot recycle gas to the gasification zone.

7. A process'of claim 1 wherein a portion of the combustible gases from the gasification zone is combined with a portion of the gases from the methanation zone to form a net product combustible gas.

8. A process of claim 5 wherein a portion of the combustible gases from the gasification zone is combined with a portion of the gases from the methanation zone to form a net product combustible gas.

References Cited UNITED STATES PATENTS 2,840,462 6/ 1958 Gorin 48-202 X 3,194,644 7/ 1965 Gorin et al 48202 X 3,471,275 10/ 1969 Borggreen 48l97 X 3,503,724 3/1970 Benson 48202 X 3,671,209 6/1972 Teichmann et a1. 48--215 2,238,367 4/ 1941' Mohr et al. 48-197 R 3,511,194 5/1970 Stookey 46-209 UX 3,702,039 11/1972 Stookey et a1 48209 X MORRIS O. WOLK, Primary Examiner R. E. SERWIN, Assistant Examiner US. Cl. X.R. 48-197 R