Catalytic gasification process

of Florham Park,

New Jersey,

UNITED STATES OF AMERICA (3) Here Insert l.Ue of Invention.

hereby apply for the grant of a Patent for an invention entitled:^<a>...........................................................

'^ASIEIGATION PROCESS • (3) Here insert • number(s) • of basic application^) • *··· (<H«relnMrt _e Name of basic

Country or • a · Countries, and • w a basic data or • · · dates which is described in the accompanying complete specification. This application is a Convention application and is based on the applications numbered**'

861,824; 861,825 and 861,826 . . _ ... . . - <«> UNITED STATES OF AMERICA for^patents or similar protection made in ..............................................................................................................

£11 on 19th December, 1977

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a aa a a a a aa a a a a a a a a jst

Our address for service is Messrs. Edwd. Waters & Sons, Patent Attorneys,

Queen Street, Melbourne, Victoria, Australia.

(9) aimsture (·) of Applicant (s) or

Seal of Company and Signatures of its Officers as prescribed by its Articles of Association.

<·>

,. 19th _t DECEMBER, 78

DATED this...............................................day of........................................................................19.............

EXXON RESEARCH AND ENGINEERING COMPANY..................................................................................

hy : S-2.S.ZZ S..................

(T. A. Barnes) . Reg’d. Patent Attorney

To:

The Commissioner of Patents.

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5' ‘9

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ft (CONVENTION. Company.) ^{Form 8}

COMMONWEALTH OF AUSTRALIA

Patents Act 1952Ί969

DECLARATION IN SUPPORT OF A CONVENTION APPLICATION FOR A PATENT OR PATENT OF ADDITION

778/78 iJirui In support of the Convention Apphcation made by⁽¹⁾..................................................

EXXON RESEARCH AND ENGINEERING COMPANY (hereinafter referrea to as the applicant) for a Patent ins’JVitic for an invention entitled:¹²'.................................................................................

of Invention.

.............................GASIFICATION .. PROCESS.......................................

(3) Here insert full Name and Address, of Company oflicia’ authorized to make declaration.

(4) Here iuftert basic Country or Countries followed by date or dates and BasicApplicant or Applicants.

.....................................................................................................

of.......................Wood.b.r4_xd.ge._&gt;....NewL.,Je.rsey_J....Hnited...State.s.pf America........................

do solemnly and sincerely declare as follows:

1. I am authorised by the applicant for the paten c to make this declaration on its behalf.

2. The basic application as defined by Section 141 of the Act was

....................................made in⁽⁴¹..Uni.t.ed...S.t.a.t.e.s...o.f. America.................................................·............

on the...............I?*»....................._day of........19?.? , by.................................................

RICHARD CHARLES NEAVEL

<td> on the........</td><td> 19th</td><td> ..............day of.......</td><td> December</td><td> ........1977...</td><td> by..........................</td><td></td>

<td></td><td> ROBERT</td><td> JOSEPH LANG</td><td></td><td></td><td></td><td></td>

<td> on the</td><td> 19 th</td><td> day of</td><td> December</td><td> 1977</td><td> » by</td><td></td>

<td></td><td> ROBERT</td><td> JOSEPH LANG</td><td></td><td></td><td></td><td></td>

.«si Here q (5) RICHARD CHARLES NEAVEL and ROBERT JOSEPH IANG of insert (in .................................-··......................................................... -·· ................................................................

full) Name andAcMivfts 220 Post Oak Lane_?Baytown, Texas and_103 Crestway_?....Baytown, Texas,

Inventor or ’ inventors. United .States ...of ..................................................................................

-’*i4 (6) Signature.

-i»/are the actual inventors of the invention and the facts upon which the applicant is entitled to make the application are as follow:

The applicant is the assignee of................................................................................................

RICHARD CHARLES NEAVEL and ROBERT JOSEPH LANG

4. The basic applications referred to in paragraph 2 of this Declaration was.....................................,................the first applications made in a Convention country in respect of the invention the subject of the application.

DECLARED at.... Xlextear Park,.. .N^....^.r.aay,....Uni.t.ed...S.t.atefl....Q.f...Araexica this...............................Z..™..................................day of..........______________-...19...7.8..

(«&gt; e:

ON RESEARCH AND ENGINEERING COMPANY “/Z . A. * (12) PATENT SPECIFICATION

ABSTRACT (19) AU (11) AU-A 42778/78

<td> (21 )</td><td> 42778/78</td><td> (22)</td><td> 21 .12.78</td><td> (23)</td><td> 21.12.78</td><td> (24) 19.12.77</td>

<td> (31)</td><td> 861824</td><td> (32)</td><td> 19.12.77</td><td> (33)</td><td> US</td><td></td>

<td></td><td> 861825</td><td></td><td> 19.12.77</td><td></td><td> US</td><td></td>

<td></td><td> 861826</td><td></td><td> 19.12.77</td><td></td><td> US</td><td></td>

(43) 28.6.79 (51) C1 OK 3/02 (54) CATALYTIC GASIFICATION PROCESS (71 ) EXXON RESEARCH AND ENGINEERING CO.

(72) NEhVEL R.C. AND LANG R.J.

(74) WM (57) CLAIM

1. A process for gasifying coal to produce a fuel gas, characterized by comprising the following steps in combination:

a) ion-exchanging a Group II-A metal onto said coal by contact thereof with a solution of a Group II-A metal compound,

b) separating the Group II-A ion-exchanged coal from said solution,

c) admixing said Group II-A ion-exchanged coal with a Group I-A metal compound, and then

d) gasifying said treated coal at gasification condition^ in a gasification zone to produce fuel gas .

D1

23.1

Form 10

COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69

COMPLETE SPECIFICATION (original:

778/ra

Clan Int. Clan

Application Number:

Lodged:

• · Complete Specification Lodged:

• · • · · · Accepted:

., Published:

* ’’Wiority:

• ••Related Art:

• · Name of Applicant:

• · · * «Address of Applicant

EXXON RESEARCH AND ENGINEERING COMPANY

Florham Park, New Jersey, UNITED STATES OF AMERICA ··&lt;&gt;··Actual Inventor:

• ·

Richard Charles Neavel and Robert Joseph Lang

Address for Service :

EDWD. WATERS &amp; SONS,

QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled:

GASIFICATION PROCESS '* ** description of this invention, including the best method of performing it known to :- us

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It was early recognized that some mineral and trace inorganic constituents naturally present in some coal could exert favorable catalytic influences in gasification reactions vis-a-vis thermal reactions, and a variety of catalytic materials have been added to coal to alter the natural chemistry inherent in various of the prior art coal gasification processes. There is a profusion of information covering catalytic coal gasification processes; both domestic and foreign, this including both patents and literature. Illustrative thereof is a recent paper by James L. Johnson; Catal. Rev.

Sci. Eng., 14(1) pp. 131-152 (1976), which includes a survey of the catalytic gasification art. Therein various materials have been characterized as generally useful catalysts for the gasification of coal, or carbonaceous solids, the survey naming various metals, metal oxides, metal halides, transition metals, and iron carbonyls. Group I and Group II metal compounds as a class, notably potassium carbonate, sodium carbonate, potassium chloride, sodium chloride, and calcium oxide are given special recognition, it being suggested that few catalysts are as effective in promoting gasification rates as alkali metals, and that none are more active. In the article,

778 /78 • · · • · ft ft ft ft

- 2 the catalytic properties of sodium and calcium are specifically discussed. Each of these cations, respectively, have been ion-exchanged into lignite, exchange being possible, and attributed to the presence of the carboxy functional groups known to be present in lignite, and other low rank coal structures. Gasification rates with steam-hydrogen mixtures were increased when sodium or calcium were added to the lignite via the exchange mechanism. However, attempts to add sodium or calcium to bituminous coals via ion-exchange were unsuccessful due, as suggested in the article, to the lack of exchange sites on high rank coals.

In a catalytic coal gasification process, i.e., one whose object is to produce high-BTU gas, steam, and particulate coal are fed to a gasifier at elevated temperature and pressure and converted to a synthesis gas, or gaseous ndrvture of high methane content, which contains significant amounts of carbon monoxide and hydrogen which must also be catalytically converted in situ or ex situ within the gasifier to methane, practical objectives require increased thermal efficiencies, with simultaneous reduction of reactor size and temperature, as well as simplification and reduction of the steps involved in the operation. It has been recognized, and is evident that these and other objectives might be obtainable by improved catalytic materials added to the mass of feed coal. Though much of the prior art disclosures relate to disclosures cf physical admixtures of a catalyst and a coal, it has been recognized that a thorough dispersion of the catalyst throughout the coal better promotes gasification rates, and activity than a physical mixture. In the past, however,

-3whereas it has not proven particularly difficult to effectively, uniformly, disperse catalytic materials throughout low rank coal structures, thie has riot been true of high rank coals, notably subbituminous and bituminous coals. This is because low rank coals have active sites which makes feasible the exchange of cations onto these sites. With high rank coals, however, the coal particle is devoid of such sites.

It has been reported by Batelle Memorial Institute, subsequent to this invention, that Batelle-treated coal has been prepared from a high rank coal, i.e., Pittsburgh No. 8 coal in Batelle Memorial Institute’s Hydrothermal Coal process by treating in aqueous sodium hyiroxide/calcium oxide (CaO) solution (0.13:1 CaO to coal) at 250”C (480°F), up to 3% of the CaO being chemisorbed on the coal. It is disclosed that at 850°C (1560°F) and 500 psig 65% of the treated coal can be converted by steam in three minutes compared with 90 minutes for untreated coal. S. P. Chauhan (Batelle Memorial Institute, Columbus Lab), K. Woodcock (E.R.D.A.) et al 173rd ACS National Meeting (New Orleans 3/20-25/77) ACS Div. Fuel Chem. Prepr. 22 #1:38-52 (1977).

There is, and remains a need for providing better catalytic coal gasification processes, or catalysts for use in catalytic coal gasification processes which are capable of producing high-BTU fuel gases from various coals, particularly high rank coals for commercial usages at improved economies, or efficiencies.

It is, accordingly, the primary objective of the present invention to supply this need.

A particular object is to provide a process for the

- 4 42ΠΖΠ8

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• · 14 • · · · -4.—τ .··. : is • · · » · • 16 • · · · • · * · .19 • · · • · : ·... 20 . 21 • · · • · ·

.....: 22 • · • 23 • · · • · · • -25 treatment of coals, notably high rank coals, or coals which have insufficient active sites to permit ion-exchange, to render such coals amenable to gasification at increased rate, particularly for use in the production of high-BTU fuel gases.

A further object is to provide, as compositions or articles of manufacture, a pretreated particulate coal feed which has been rendered amenable to gasification by treating to form therein relatively inexpensive species of Group I-A or Group II-A metals, or admixtures thereof, in high concentrations .

These objects and others are achieved in accordance with the present invention embodying a novel process, and the articles of manufacture, or compositions, formed thereby, wherein a Group II-A metal (Periodic Table of the Elements, Sargent-Welch Scientific Company_; Copyright 1968), or compound thereof, can be ion-exchanged onto coal, and thereafter a Group I metal admixed or otherwise incorporated therewith, so that the composition can be pyrolyzed, and gasified, to form a high-BTU, intermediate-BTU, or synthesis fuel gas. Suitably, the Group II metal, or alkaline earth metal, can be directly ion-exchanged onto a low rank coal, without necessity of any pretreatment, by contact with a solution of a Group II-A metal compound, preferably a basic solution of said compound; since, of course, low rank coals contain natural ion-exchange sites. An alkaline earth metal, or metals, can also be ionexchanged onto a high rank coal, notably one deficient in natural active exchange sites, such as a subbituminous or bituminous coal, by (a) contacting and soaking the coal in an alkali solution comprising a Group I-A metal compound or an admixture of Group I-A and Group II-A metal compounds, pre2 ferably a hot solution of such compounds sufficient to in3 corporate said metal compound, or cation portion thereof, into said coal and form ion-exchange sites, (b) or by oxidation of the high rank coal by contact with an oxidizing agent, prefer6 ably an oxygen-containing gas (air), peroxygen compound, oxi7dizing acid or the like, to form ion-exchange sites, and ion81·’ exchanging a Group II-A metal onto the active sites thus cre9g*q ated, and thereafter admixing or otherwise incorporating a

10^ Group I-A metal, or alkali metal, therewith to form the dell sired article of manufacture, or composition. The composition • · · • · · ’·*..* 12 can be pyrolyzed, and gasified, to form a high-BTU, inter• · • *··· 13 mediate-BTU or synthesis fuel gas. Enhanced gasificatiov rates • · : ·... 14 are achieved by gasification of the so-treated coal, or com• * ·**·.ζ 15 position which contains both the Group II-A and Group 1-A • · metals, as contrasted with a composition otherwise similar • • · · · except that it contains an equal molar quantity of either a

Group II-A metal or Group I-A metal, rather than both metals.

·’·*’· 19 Moreover, the Group I-A or Group II-A metals can act as a sul• · : 20 fur absorbent during the gasification or pyrolysis.

.··. j 21 It is essential initially to incorporate a Group II-A • · ·

.....: 22 metal, or metals, onto a coal via ion-exchange. This is con• · ’ 23 veniently accomplished with low rank coals, or coals which ······ *_e * 24 have adequate ion-exchange sites, by contacting and soaking • · · • · · the coal, suitably in particulate form, in a dispersion, or solution of a Group II-A metal compound, preferably an aqueous hydroxide solution containing sufficient of the Group II-A metal compound to exchange all the available sites and impart

<td> 1</td><td> from about 0.1 to about 10 atomic percent, preferably from</td>

<td> 2</td><td> about 1 to about 8 atomic percent, of the Group Il-A metal on-</td>

<td> 3</td><td> to the coal, based on the carbon present in the char after it</td>

<td> 4</td><td> is pyrolyzed and devolatilized. Suitably, the treatment is</td>

oo

Cf conducted at temperatures ranging from about 20°F. to about oo

230®F.·, preferably from about 40°F. to about 90°F·, suitably for periods ranging at least about 1 hour, preferably from

8^3* about 1 hour to about 72 hours, more preferably from about 24

<td> 9</td><td> hours to about 48 hours, when the temperature of the solution</td>

<td> 1C</td><td> is maintained within the expressed preferred ranges . The</td>

<td> 11 ··</td><td> period of contact, or soak, is not critical, and lesser soak</td>

<td> • · 12</td><td> periods can be employed as coal particle size is decreased.</td>

<td> *··· 13</td><td> High rank coals, though lacking in natural ion-ex-</td>

<td> *... 14</td><td> change capacity (compared to low rank coals), to permit sub-</td>

<td> is</td><td> stantial direct ion-exchange of a Group II-A metal onto the</td>

<td> .:.. 16</td><td> coal, can also be treated to form Group II-A metal ion-ex-</td>

<td> • · 17</td><td> changeable sites, or sites on which Group II-A metal cations</td>

<td> 18</td><td> can be exchanged. In one embodiment, a high rank coal is</td>

<td> .··. lg</td><td> treated with a solution of a Group I-A metal compound to form</td>

<td> *... 20</td><td> the necessary sites necessary for exchange therewith of Group</td>

<td> \ : 21 • · ...: 22 •</td><td> II-A cations. Suitably, in accordance therewith, a particulate coal containing less oxygen in an active form than would be</td>

<td> • 23 • . : 24</td><td> required to impart from about 2 to about 10 wt. percent calcium ion is contacted and soaked in an alkali solution com-</td>

<td> • · 25</td><td> prising a Group I-A metal compound, or compounds, preferably</td>

<td> 26</td><td> an aqueous alkali hydroxide of from about 0.25 to about 5</td>

<td> 27</td><td> normality, more preferably from about 0.5 to about 2 normality,</td>

<td> 28</td><td> at conditions sufficient to form active sites onto which can</td>

.. - 7 - . .

a -3 be exchanged between about 5 x 10 to about 8 x 10 gram atom equivalents of a Group I-l· metal, preferably from about

- 3 -3

1 x 10 to about 5 x 10 gram atom equivalents of a Group I4 A metal. Suitably, the treatment is conducted at temperatures ranging from about 20°F. to about 250°F., preferably from go

CI about 40°F. to about 90°F., suitably for periods ranging at oo

7least about 0.1 hour, preferably from about 0.25 hour to about δ*’ 12 hours, more preferably from about 0.25 hour to about 2 hours CM*

9*SJ*when the temperature of the solution is maintained within the 10 expressed preferred ranges. The period of contact, or soak, , .. 11 is variable and lesser soak periods can be employed as temper• · · • · · • ·· 12 atures are increased and as particle size is decreased. The • · • ·

I *** 13 coal can be treated in a single step using a solution within • · • *··· 14 which both the Group I-A and Group II-A metal compounds are • · · : 15 dispersed, or dissolved, or in multiple steps wherein the • · .:.. 16 coal is first contacted with a solution of Group I-A metal com• · · · pound, or compounds, thence with a solution which contains the Group II-A metal compound, or compounds . The coal within • · · ‘ *·*··* 19 which ion-exchange sites (i.e. Group II-A cation exchangeable • · • ··· 20 sites) have been created is then, in ons embodiment, separated : 21 from the alkali solution of the Group I-A metal compound, or • · · ·;···· 22 compounds, and then contacted and soaked with a solution, , 23 dispersion or slurry, preferably an aqueous solution of from • ·

.. . 24 about 0.25 to about 5 normality, preferably from about 0.5 to • · · about 2 normality, of a Group II-A metal compound, or compounds sufficient to exchange at least a portion of the Group I metal cations with Group II metal cations . Solution temperatures ranging from about 20°F. to about 200°F., preferably from

- 8 1 about 40°F. to about 90°F., have been found satisfactory for ion-exchange and replacement of Group I-A metal cations by

Group II-A metal cations . The period of treatment is not critical, but generally requires at least about 1 hour, suit5 ably from about 0.25 hour to about 48 hours, and preferably from about 1 hour to about 8 hours for adequate exchange at

7the preferred conditions. Faster exchange rates can be

OO

8^_ achieved by increasing the temperature of the solution and 9decreasing the particle size.

10xj* In forming the novel compositions, or articles of manufacture, of this invention, suitably from about 1 percent j*;*’;12 to about 10 percent, preferably from about 3.5 percent to about • · · ;·. 13 7 percent, of the Group I-A metal, or metals, calculated as • ··· ··. 14 metallic metal based on the weight of the coal (MAF), is in• ···

.. .15 corporated onto the coal, and from about 1 percent to about • · · • · · * *16 10 percent, preferably from about 3 percent to about 5 per• · · ·

...I 17 cent of the Group I-A metal cation, calculated as metallic metal based on the weight of the coal (MAF), is then replaced . .p 19 with a Group II-A metal, or metals, via ion-exchange. Suit• · · ··. 20 ably therefore, the coal is one which contains, after treatto · · · • 21 ments with the solution, or solutions, a sum-total of from ·· · to · · **22 about 1 percent to about 10 percent, preferably from about 3.5 • · · · · · . 23 percent to about 7 percent, of Group I-A and Group II-A metals, •J·*··;24 calculated as metallic metal based on the total weight of the ·· · *· *.Σ25 coal (MAF). From about 0.5 percent to about 4 percent, pre26 ferably from about 0.5 percent to about 2 percent, of the total metal is thus characterized as a Group I-A metal, or metals, and from about 0.5 percent to about 6 percent, prefer- 9 1 ably from about 3 percent to about 5 percent, as a Group II-A metal, or metals .

Alternatively; a high rank coal, notably a sub4 bituminous or bituminous coal, can be contacted with an al5 kali solution of an admixture of compounds of Group I-A and

Group II-A metals, preferably a hot solution of such compounds, inclusive of a soluble alkali metal salt and an alkaline earth oo metal hydroxide, each of which interacts one with the other to

9^ form an alkali metal hydroxide, and an insoluble alkaline

1(?Μ* earth metal salt precipitate. The coal is treated in a single 11 step by contact with the solution within which both the Group • »· • · ·

·.·..· 12 I-A and II-A metal compounds are dispersed, or dissolved.

• · ! *...13 Where the coal dc t not contain adequate ion-exchange sites, ·*·...14 these are formed by reaction between the alkali metal hydrox• .··, ; 15 ide generated by the reaction, and the coal, and in turn all • · · • · . 16 or a portion of the alkali metal cations are exchanged or re17 placed by excess alkaline earth metal cations which are pres18 ent in the alkali metal hydroxide that is formed. Preferably, the treatment is continued until substantially all of the ·*·.,. 20 alkali metal cations have been replaced by the alkaline earth

.. . 21 metal cations, and then the solution is evaporated while in • · · • · · . 22 contact with the coal to redeposit and physically disperse • · • 23 the alkali metal upon the coal.

······ • · 24 The presence of the alkali metal hydroxide formed ·· · • · · by the interchange permits the formation within the coal of reactive sites, or ion-exchange sites on which the alkaline earth metals can be exchanged, but the sites are created from an alkali metal hydroxide formed in situ from an interaction

1 between an inexpensive alkali metal salt and an inexpensive alkaline earth metal hydroxide. For example, it is known .

that active sites are formed on coal by direct contact and treatment with a sodium hydroxide solution, but sodium hydrox5 ide is rather expensive. Sodium carbonate, however, is rather ' 6 inexpensive as is lime, and hence sodium carbonate, Na2COj, £2 can be dissolved in water and hydrated lime, Ca(OH)2&gt; added

8°O thereto, such that sodium hydroxide is formed in situ from C''- .

the alkali metal carbonate as a source of sodium ions and 10⁶^. the alkaline earth metal hydroxide as a source of hydroxyl ions. CaCO« precipitates out. In such solution the sodium • ·· J • · ·

*.·..· 12 hydroxide reacts with the coal to form ion-exchange sites, • · ϊ *·.. 13 and as these sites are formed, alkaline earth metal cations ·*·,,. 14 from excess dissolved Ca(0H)2 are exchanged thereupon as con.··. J 15 tact of the coal with such solution is continued.

• · · • ·

Sufficient of the alkaline earth metal cations are • · · · contained within the solution for substantial exchange and replacement of the alkali metal from the coal at ambient con·*·**· 19 ditions by soaking the coal in the solution for a period rang• · ; 20 ing at least about 0.25 hour, suitably from about 1 hour to

.. . 21 about 100 hours, preferably from about 24 hours to about 96 • ·· hours. The contact period, however, can be decreased by re• · • 23 duetion of the temperature. Thus, lime is not very soluble, * 24 especially in basic solution and an insoluble calcium carbon• · · * * 25 ate precipitate is formed such that relatively few calcium ions are present in the solution. However, sufficient of the calcium cations are maintained in solution for reasonably rapid exchange of calcium onto the active sites to produce

1 acceptable gasification rates, and methanation activity,by elevating the temperature of the solution.

In one embodiment, a particulate coal containing less oxygen in an active form than would be required to im5 part from about 1 to about 10 wt. percent calcium ion, particu6 eo larly a bituminous coal, is contacted, heated or boiled and C;

7ς© soaked in an alkali solution comprising an admixture of com8^ pounds, inclusive of a soluble alkali metal salt and an al9^ kaline earth metal hydroxide in excess of that amount re10 quired to react to form an alkali metal hydroxide and an in11 soluble alkaline earth metal salt precipitate. The solution • 99 • · ·

*.·..· 12 formed, preferably with water as a solvent, is characterized • 9 • *··· 13 as an aqueous alkali hydroxide of from about 0.1 to about.10 ·*·... 14 molarity, preferably from about 0.5 to about 2 molarity, •

»·*. ϊ 15 and this solution is maintained in contact with said coal at

99 • 9

.... 16 conditions sufficient to form active sites onto which can be ···· Δ □ exchanged between about 5 x 10 to about 8 x IO* gram atom equivalents of a Group I-A or Group II-A metal, or both, per ·*·’*· 19 gram of coal, preferably from about 1 x 10” to about 5 x 10” • 9 : *... 20 gram atom equivalents of a Group I-A or Group II-A metal, or .·* · 21 both per gram of coal. Siitably, the treatment is conducted

99

.....: 22 at temperatures ranging from about 20°F. to about 250°F·, • 9 • 23 preferably from about 180°F. to about 220°F·, suitably for

999999 * 24 periods ranging from about 0.1 to about 48 hours, preferably • 9 9 from about 0.25 hour to about 6 hours, more preferably from about 0.25 hour to about 1 hour, when the temperature of the solution is maintained within the expressed preferred ranges .

Group II-A cation exchangeable sites can also be

- 12 1 formed in high rank coals by partial oxidation of the coal.

Particulate coals are oxidized by contact with an oxygen-con3 taining gas (air) peroxygen compounds inorganic or organic peroxides, oxidizing acids and the like. Exemplary of such compounds are hydrogen peroxide, organic and metal peroxides, alkali metal permanganates, hypochlorite, nitric acid, sul7 furic acid and the like. The coal within which Group ΙΪ-Α 3 eocation exchangeable sites have been created is then contacted • ·· * · 4 ·» » 4 • · · • ··· ···· • ·· • · 9 ·* • · • · • ··· ·· · • · · c^and soaked with a solution, dispersion or slurry, preferably ^an aqueous solution of from about 1 x 10 molarity to about

C*45 molarity, preferabl r from about 1 x 10 molarity to about

--Λ2 molarity, of a Group II-A metal compound, or compounds suf13 ficient to exchange Group II metal cations into the structure.

Solution temperatures ranging from about 2D°F. to about 230°F., preferably from about 40°F. to about 90°F., are satisfactory for ion-exchange of Group II-A metal cations into the struc17 ture. The period of treatment generally requires at least about 1 hour, suitably from about 1 hour to about 72 hours, and preferably from about 24 hours to about 48 hours for ade20 quate exchange at the preferred conditions.

Formation of the composition suitable for pyrolysis, or gasification, is then completed by physical incorporation, or admixture, of the Group I-A satai compound with the

Group n-A containing coal. In forming the novel compositions, or articles of manufacture, of this invention, suitably from about 0.1 atomic percent to about 10 atomic percent, prefer27 ably from about 0.5 atomic percent to about 3 atomic percent, of the Group I-A metal, or metals, based on the carbon

- 13 1 present in the coal char formed by pyrolysis or devolatilization is incorporated with the Group II-A ion-exchanged coal. The composition is thus one which contains, after treatment, a sum4 total of from about 0.2 atomic percent to about 20 atomic per5 cent, preferably from about 1.5 atomic percent to about 11 atomic percent, of Group II-A and Group I-A metals, based on carbon present in the coal char formed by pyrolysis or de8 volatilization.

S2

9&lt; The process of this invention is generally appliOO lO^cable for the incLusion of Group I-A and Group II-A metals in

11*~ virtually anv rank of coal, including lignite, brown coal, _β·_β«· 04 '

·.·..· 12^*peat, and the like, subbituminous coals such as Wyodak and • · • “··· 13 the like, and bituminous coals such as Illinois No. 6, ·*·... 14 Pittsburgh No. 8 and the like. The process, however, has .··. J 15 special utiLity in the treatment of the high rank coals, • ·· • · • 16 notably the subbituminous and bituminous coals which have in• 999 ^J sufficient natural sites to permit high per se dispersion of the Group I-A and Group II-A metals into the structure.

*’·’*· 19 Suitable Group II-A metals, or alkaline earth metals, : 20 suitable for the practice of this invention are exemplified by

·. · 21 magnesium, calcium, strontium and barium, the effectiveness • ·· of which for gasification purposes increases directly with in• · • 23 creasing atomic weight except for calcium which is a highly ’

“ ‘24 preferred species of Group II metal based on its cost effect• 9 9 * ** 25 iveness, and exceptional reactivity. The alkaline earth metals are suitably employed in solution as salts, preferably as weak acids, and hydroxides illustrative of which are magnes28 ium carbonate, calcium hydroxide, strontium oxalate, barium

1

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• · 13 a a a a ·· »15 • · · • · · ’ . *16 • · · ·

...J ₁₇ • · · :·. 20 • · · · .: .21 • · · • · ·

......22 • · . 23 ·:···: 24 • · · • · · • 25 acetate and the like. Suitable Group I-A metals, or alkali metals, are exemplified by lithium, sodium, potassium,rubidium and cesium, the effectiveness of the metals as gasification catalysts increasing in direct proportion to their increased atomic weight, though sodium and potassium are preferred metals based on cost-effectiveness . These are suitably employed a&amp; salts or hydroxides, e.g., sodium carbonate, potassium hydroxide, potassium nitrate, cesium acetate and the like .

Group I-A metals, or alkali metals, suitable for the practice of this invention are exemplified by lithium, sodium, potassium, rubidium and cesium, the effectiveness of the metals as gasification catalysts increasing in direct proportion to their increased atomic weight, though sodium and potassium are preferred metals based on cost-effectiveness. These are suitably employed as salts or hydroxides, e.g., sodium carbonate, potassium hydroxide, potassium nitrate, cesium nitrate and the like. In the embodiment of this invention which requires the treatment of the coal with' an admixture of Group I-A and Group II-A compounds, virtually any alkaline earth metal hydroxide or alkaline earth metal compound which will decompose and form a hydroxide in situ, can be employed in the practice of this invention. Exemplary of such compounds are hydroxides formed from magnesium, calcium, strontium and barium, with calcium being preferred. The alkali metal salt is constituted of any of lithium, rubidium, cesium, but particularly sodium or potassium, in combination with an anion which provides a soluble salt, and forms an in- 15 • ·· • · • ·· · ·«··

<img file="AU4277878A_D0005.tif" />

<img file="AU4277878A_D0006.tif" />

soluble molecular species with the specific alkaline earth metal of the alkaline earth metal hydroxide employed in the admixture added to the solvent. Exemplary of alkali metal salts suitable for use in the practice of this. invention are sodium bicarbonate and sodium carbonate which form an insoluble salt on reaction in solution with barium, strontium or

7qq calcium; sodium oxalate, potassium oxalate which form an in8** soluble salt on reaction with barium, strontium or calcium; tr—

9C4 sodium chromate or cesium chromate which form an insoluble precipitate on reaction in solution with barium or strontium; sodium fluoride which forms an insoluble precipitate with strontium; and the like.

In the past, low rank coals have been successfully treated via ion-exchange with alkali or alkaline earth metal caticns, including, e.g., sodium or calcium, because of natural exchange sites. The exchange of alkali or alkaline earth metal cations, particularly the latter, onto bituminous coals, however, has been ineffective because of the nature of bituminous coals which are lacking in natural exchange sites. In accordance with the present process, nonetheless, ion-exchange sites are created in the coal by oxidation of the coal or treatment with a strong alkaLi solution of Croup I-A metal compounds or the solution which is generated by reaction between the admixture of the soluble alkali metal salt and alkaline earth metal hydroxide, this making feasible the addition, or incorporation of considerably greater amounts of alkaline earth metal cations into the coal than heretofore believed possible. Whereas substantially complete exchange of ·- . - 16 - / . ' ' ' ^; / ' &lt;

alkaline earth metal into the created ion-exchange sites is possible, the presence of both alkali and alkaline earth metal cations in the coal is highly preferable for it has been found that gasification rates are considerably higher for a coal which contains both types of metal vis-a-vis a coal similarly ^treated, and otherwise similar except that it contains either °°an alkali metal or alkaline earth metal to the substantial ext'— elusion of the other. After complete exchange and replacement ^of substantially all of the Group I-A metal by a Group II-A metal, in any event, the Group I-A metal can be physically dispersed upon the structure to provide a highly reactive feed • · · • · · for use in gasification reactions.

• · • *··· 13 Gasification processes as generally known in the • ·

Z ·... 14 art can be improved with respect to yield or conversion rate, • * ζ**·.· 15 or both, when the process of this invention is employed in • · .j.. 16 the formation of the novel carbonaceous feed compositions .

• · · ·

The compositions are reacted with a gaseous species or a mix18 ture of gaseous species at elevated temperatures, and general··*·’*· 19 ly elevated pressures to produce and optimize the composition • ·

J ‘...20 of the fuel gases. The gaseous species generally employed as .··. ·21 reactants include oxygen, steam, hydrogen, and carbon oxides • ··

.....; 22 such as carbon dioxide. Generally, temperature, pressure, • · * .23 flow rate, mole ratios and relative mole ratios depend on the *_e ’24 specific process employed and the actual products desired • · · • · · therefrom. In any event, the composition of the gaseous pro26 ducts are altered by the particular catalyst employed. For example, the products resulting from the gasification of coal with steam is enriched in methane by judicious selection of the

- 17 1 optimum alkali and alkaline earth metal, and concentration thereof within the feed composition, to promote the conversion of carbon monoxide and hydrogen to methane. Generally sodium or potassium in relatively high concentration are most pre5 ferred when maximum methane production from gasification by steam is desired, and calcium in high concentration is most preferred when production of carbon monoxide and hydrogen by oo

8t- steam gasification is desired. Gasification is generally ac9^ complished by contacting the treated coal with steam at a

10^ temperature within the range from about 750°F. to about 1850°F. 11 at a steam flow rate within the range from about 0.2 to about • · · • · ·

·.·..· 12 100 W/W/Hr. Pressure is not critical, but generally ranges • · • *··· 13 from about 0 to about 1000 psig.

These and other features of the present invention •

.*·. : 15 will be better understood by reference to the following demon• · · • · strations which involve treatment of coals with Group II-A • · · · and Group I-A metals, and runs conducted by gasification of the coal with and without benefit of treatment with the al·’·’*· 19 kaline earth and alkali metal compounds and salts, particular• · ; ·... 20 ly with reference to comparative data showing gasification of .··. . 21 coal pretreated with both alkali and alkaline earth metal com• · ·

.....; 22 pounds and salts in accordance with this invention. All units • · • 23 are in terms of weight unless otherwise specified.

^: 24 EXAMPLES 1-3 • · · I. »111 I— • · · • · · ·

Samples of three low rank coals, Wyodak, Arkansas lignite and Beulah lignite, respectively, were individually treated with portions of an alkaline earth metal and with an alkali metal, respectively, and with a combination of both of

- 18 1 these metals. In treating a coal specimen with the alkaline earth metal, the coal was contacted with a saturated aqueous solution of calcium hydroxide and the treatment continued at ambient conditions until the maximum amount, which was in the range of 7-11 wt. percent calcium, had been exchanged onto the coal. In one demonstration, a portion of Wyodak coal was

7qq treated with acetic acid (HAc) to remove any natural alkali

8^’ or alkaline earth metal, while in others the coal was raw, or t''9q4 untreated. Sodium or potassium, respectively, in the weight proportions indicated in Table I, was physically admixed with the treated or untreated coal specimens and in some cases, • · · • · · *·*··’ 12 water was also added. The various specimens were then pyro• · ; *··· 13 lyzed at 1400°F. and the char subjected to steam gasification • · : *...14 at essentially identical conditions, averaging 7.5 grams of

<td> .··. : 15 • · ·</td><td> steam per gram of carbon, per hour,</td><td> at 1300°F.</td><td> and 1400°F.,</td>

<td> .:.. 16 •</td><td colspan="2"> respectively, with the following results:</td><td></td>

<td> • · · · 17</td><td> TABLE I</td><td></td><td></td>

<td> 18</td><td></td><td colspan="2"> Gasification Rate-7,/Hr.</td>

<td> . .. Ιθ</td><td> (Avg</td><td> . for 0-90%</td><td> Carbon Conversion)</td>

<td> -.-..-20</td><td></td><td> TWT</td><td> 1400^UF.</td>

<td> 2i</td><td> Wyodak + 10% K₂C0₃</td><td> 140</td><td> 218</td>

<td> . 22</td><td> Ca-Wyodak + 5% NaXC0₃</td><td> 119</td><td> 255</td>

<td> ·· · 23</td><td> Wyodak + 5% K₂C0₃^J</td><td> 107</td><td> 223</td>

<td> • ·· 24</td><td> Ca-Wyodak</td><td> 87</td><td> 161</td>

<td> .....; 25</td><td rowspan="2"> Wyodak 4- 5% Na₂C0₃ HAc-Wyodak + 5% Na₂CO₃</td><td> 86</td><td> 226</td>

<td> • *26</td><td> 63</td><td> 113</td>

<td> * 27 •</td><td> Raw-Wyodak</td><td> 63</td><td> 119</td>

<td> 128</td><td> Ca-Ark. Lig. + 5% Na^COo</td><td> 143</td><td> 243</td>

<td> • · · 29 • · · *- &gt;</td><td> Arkansas Lignite</td><td> 92</td><td> 190</td>

<td> 30</td><td> Ca-Ark. Lig.</td><td> 83</td><td> 163</td>

<td> 31</td><td> Ark. Lig. + 5% Na₂CO₃</td><td> 62</td><td> 130</td>

<td> 32</td><td rowspan="2"> Beulah Lig. + 5% Na₂C0₃ Ca-Beulah + 5% Na₂c6₃</td><td> 126</td><td> 180</td>

<td> 33</td><td> 97</td><td> 191</td>

<td> 34</td><td> Beulah Lignite ^J</td><td> 84</td><td> 160</td>

<td> 35</td><td> Ca-Beulah</td><td> 62</td><td> 141</td>

<img file="AU4277878A_D0007.tif" />

to··· to to to to ·· ι &lt;

• · • · • · • ··· •

• to · • · to to ·· •

<img file="AU4277878A_D0008.tif" />

These data clearly show that the three coals behave differently . Sodium and calcium individually and in combina3 tion, promote the activity of raw Wyodak coal. With Arkansas lignite, however, sodium and calcium, individually, decrease the gasification rate. The combination of both sodium and calcium, however, increases the gasification rate of the raw coal, and this is true regardless of the temperature. These

OO

8data clearly shown synergism between the sodium-calcium .com£ * bination. With Beulah (North Dakota) lignite, calcium alone

Cm lO^hurts the gasification rate compared to the raw coal. Sodium alone is a better catalyst than the sodium-calcium combination at 1300°F., but not at 400°F.

The attached figure shows diagrammatically the pro14 motional effects of various alkali metals on calcium-exchanged

Wyodak coal containing about 87_O Ca. The alkali metals were · added as carbonates before pyrolysis. The broken curves, for comparison, show the gasification rates measured with I^CO^ on raw Wyodak coal containing about 1% naturally occurring Ca .

The promotional effects are seen at 1300°F. at low alkali metal loadings. The promotional effects are seen at 1400°F., with Na, K and Cs, over a wider range of loadings, and the ef22 fects are more pronounced. It will be particularly observed that inexpensive Na compares very favorably with K in its pro24 motional effect on gasification rate.

The following example demonstrates that the methana26 tion activity of the sodium-calcium catalyst i.^c better than that of a coal which contain calcium alone, and its perform28 ance is not surpassed even by potassium carbonate, a known

- iu » • · · • ft • · • ··· • ft • ft ⁷5

8°°

9t10, ’:i2 • ·· • ft ft ft ft ft ft ft ft ft • ftftft ft • ft ft ft ft ft ft ·· ft ft ft ft ft ft ft • ft ft ft ft ft ··

21 22 outstanding catalyst with high commercial potential.

EXAMPLE 4

A sample of Illinois No. 6 coal was oxidized by treatment at 70-96°F. by soaking in a 3 wt. percent aqueous hydrogen peroxide solution, until the heat released indicated 2 wt. % of the carbon had been oxidized. This oxidized coal was soaked in saturated Ca(0H)2 solution until the maximum amount of calcium ion was taken up by ion exchange. This material was dried and split into two portions. One portion was pyrolyzed at 1400°F., the resulting char containing 2.4 atomic % Ca/carbon. The other portion was admixed with ^2^3 before pyrolysis at 1400°F. so that the resulting char contained 0.9 atomic % Na/carbon in addition to the calcium. Measurement was made of the amount of methane produced at different levels of conversion of the coal with steam. The results are given in Table II.

TABLE II

Percent Steam Conversion Gaseous Carbon as Methane, Mole %

Potassium Alone

<td> 25-</td><td> 7</td>

<td> 44</td><td> 17</td>

<td> 49</td><td> 24</td>

<td colspan="2"> Calcium Plus Sodium</td>

<td> 26</td><td> 13</td>

<td> 29</td><td> 14</td>

<td> 32</td><td> 16</td>

These data show that the methane production of the sodium-calcium combination is at least as good as with potassium carbon at a given steam conversion.

The alkali-promoted alkaline earth catalysts are believed as effective with coal-derived products such as lique- 21 1 faction bottoms and also with other gasifying agents such as hydrogen and carbon dioxide.

³ EXAMPLES 5-9 '4 In a further series of runs, to show the effect of different alkaline earth metals on coal for use in forming the compositions of this invention for gasification, the maxi7 mum amount that would be taken up of various alkaline earth °°metals (i.e., 7.8 wt. % Ca or equivalent quantities of the t-·others) were ion-exchanged onto portions of Wyodak coal and ^^the compositions gasified. Certain compositions were further formed by taking portions of these ion-exchanged samples and • ·· ·,·..· 12 physically admixing 5 wt. % sodium carbonate therewith, and • · ί ·... 13 the compositions then gasified. One specimen was treated with

<td> :·. 14 « ft® ·</td><td colspan="2"> acetic acid to remove natural ion-exchanged metals.</td><td> The re-</td>

<td> ·· · 15 • ft ft</td><td> suits are shown in Table</td><td> III.</td><td></td>

<td> • ft . 16 ft···</td><td></td><td> TABLE III</td><td></td>

<td> ...i ₁₇</td><td colspan="3"> COMPARISON OF SODIUM PROMOTED ALKALINE EARTH CATALYSTS</td>

<td> 18</td><td></td><td colspan="2"> Gasification Rate-%/Hr.</td>

<td> 19 • ··</td><td></td><td> 13mm</td><td> 1400 F.</td>

<td> ft · · • ’· 20</td><td> Ca-Wyodak + 5% Na₉C0_a</td><td> 119</td><td> 225</td>

<td> 21</td><td> Sr-Wyodak + 57. Na^CO,</td><td> 90</td><td> 199</td>

<td> * /”22</td><td> Ba-Wyodak + 57. Na^CO</td><td> 86</td><td> 163</td>

<td> .. .23</td><td> Mg-Wyodak + 57. NaXCO:?</td><td> 89</td><td> 153</td>

<td> ·. ’.Ϊ24</td><td> HAc-Wyodak + 57. Na₂CO₃</td><td> 63</td><td> 113</td>

<td> ·:···: 25</td><td> Ca-Wyodak</td><td> 87</td><td> 161</td>

<td> • 26</td><td> Sr-Wyodak</td><td> 73</td><td> --</td>

<td> .....:27</td><td> Ba-Wyodak</td><td> 66</td><td> --</td>

<td> • ‘28</td><td> Mg-Wyodak</td><td> 27</td><td> 64</td>

<td> .··. :29 ft ··</td><td> HAc-Wyodak</td><td> 8</td><td> 15</td>

<td> 30</td><td colspan="2"> These data show that ion-exchanged Mg, Ca,</td><td> Sr and Ba</td>

<td> 31</td><td colspan="3"> all catalyze the steam-gasification of Wyodak ccal when these</td>

<td> 32</td><td> specimen are compared to</td><td> the specimen which has been</td><td> acetic</td>

- 22 1 acid extracted to remove natural calcium. When 5 wt. % sodium carbonate was added to these samples, the gasification rate increased in each case. The specimens which contained both calcium and sodium provided the best results, and it is noteworthy that at 1300°F., this gasification rate of 119%/hr.

cannot be reached by adding sodium carbonate to raw Wyodak coal in reasonable amounts. With 10 wt. % sodium carbonate,

Q^raw Wyodak gasifies at a rate of 105%/Hr. at 1300°F., and ©'“with 20% it gasifies at 109%/hr.

1+» ¹⁰ 04 The promotional effects of various alkali metals on ^ion-exchanged Wyodak coal containing alkaline earth metals • 9 9 · 9

·.·..· 12 show considerably improved gasification rates. At 1300°F.

• *··· 13 the promotional effects are seen at relatively low alkali

J *..,14 metal loadings, and at 1400°F., the effects over a wide range »··.. ϊ 15 of loadings are even more pronounced. Methanation activity is

9 also improved.

EXAMPLE 10

A 15 g. portion of -16 +20 mesh (NBS) Illinois high -*•’’•19 volatile C bituminous coal was boiled for 3.5 hours in an aq9 · ί ’...20 ueous 1 normal NaOH solution. The specimen was then soaked in ·· .21 several hundred ml of distilled water for several hours. The «9

99

.....:22 specimen was then soaked for several days in about 5 g. of

9 • .23 Ca(OH)2 and fresh distilled water. Excess, unutilized Ca(0H)2 ’ *24 was elutriated from the coal specimen.

9 9

Analysis of treated coal specimen indicated 5.1 weight percent calcium on the impregnated coal specimen. In contrast, soaking coal not pretreated with NaOH in Ca(0H)2 re28 suited in an uptake of only 1.9 weight percent calcium.

- 23 1 (Boiling a sample of the coal in Ca(0H)2 solution with ex2 cess powdered Ca(0H)2 did not enhance the calcium uptake).

The steam gasification rate at comparable conditions was 1.8 times higher for the Na0H/Ca(0H)2 treated composition than for the Ca(0H)2 composition.

The following example contrasts the difference in 7^2 uptake of a Group II-A metal from a specimen of coal pre8P° treated with an aqueous solution of a Group I-A metal vis-a' 9t— vis uptake of a Group II-A metal by an untreated, but otherCM wise similar coal specimen.

EXAMPLE 11 • ft ft ..............

• · · *»*··* 12 A 5 g. sample of the same coal specimen as used in • * • · ; ··’ 13 Example 10 was soaked for 64 hours in 2 normal aqueous NaOH at ’··. 14 ambient temperature (approximately 76°F). The specimen was »*\j 15 cleared of NaOH and soaked for 55 hours in water containing • · several grams of Ca(OH)2 powder. Excess, unutilized Ca(OH)2 ft··· powder was elutriated from the specimen. The sample was found to contain, after treatment, 4.5 weight percent calcium.

t ··

*.·..· 19 In contrast, a similar coal specimen soaked in • · i ·.·. 20 Ca(OH)2 only without an NaOH pretreatment took up 2.1 weight .··. J 21 percent calcium. Additional tests have established that NaOH • ·· .····! 22 treatments as short as 2 hours at room temperature allow sub* * 23 sequent calcium uptake of greater than 4 weight percent.

« 24 In accordance with the following data a bituminous ft ft ft ft ·· .

coal is treated simultaneously with the Group I-A and II-A metal.

EXAMPLE 12

A 5 g. specimen of the Illinois coal of Examples 10 li+ ft ft ft ··· • · · · • ·· ft · ft and 11 was soaked in 52 ml of 1 normal aqueous NaOH containing

0.13 g. powdered Ca(OH)2 (equivalent to 1.4 weight percent cal3 cium on coal) for 89 hours at room temperature. Excess NaOH and

Ca(OH)2 were removed with distilled water. The treated sample contained 2.6 weight percent sodium and 1.0 weight percent calcium.

When gasified under conditions identical to those in

00Example 10, the steam gasification rate was 4.5 times that obC-9|^.tained for the sample exchanged only with Ca(0H)2 and 2.5 10^, times the rate obtained on the specimen that was boiled in

NaOH and then exchanged with calcium.

EXAMPLE 13

In a series of runs, portions of Illinois No. 6 coal, a bituminous coal, were treated with aqueous solutions, or slurries of admixtures of sodium carbonate and/or lime, at solution boiling temperature, then soaked at ambient tempera17 ture for varying time periods. It was observed that sodium hydroxide was formed and calcium carbonate was precipitated.

The sodium hydroxide was found to attack the coal to form sodi20 um ion-exchanged sites, while excess calcium hydroxide dis21 solved such that calcium ions were exchanged for the sodium ions . Since the hydroxyl ion was found to suppress the solu23 bility of the calcium hydroxide somewhat, a soak time was neces24 sary to achieve adequate calcium ion exchange for the sodium.

All of the sodium left in solution was distributed by drying and pyrolysis to form the active sodium promoted calcium cata27 lyst.

For comparative purposes, portions of the coal were

- 25 1 also physically admixed with various weight portions of potas2 sium carbonate, a catalyst of known high commercial potential for use in the treatment and gasification of coal. Also, a portion of the coal was treated with a physical admixture of sodium carbonate, and a similar portion of the coal was soaked in a lime slurry. These several treated coal specimens were then dried and gasified at 1300°!’., ambient pressure, by in8jg jection of steam to provide an average steamtcarbon ratio of 9oO 7.5 W/W/Hr.

10^ The weight percent of the potassium carbonate, and

11C4 the weight percent of the sodium carbonate or calcium oxide,

<td rowspan="2"> • • • • • · • • •</td><td rowspan="2"> • · • · • · ·· • ···</td><td rowspan="2"> 12 13 14</td><td colspan="5"> or both, in terms of weight percent on coal;</td><td colspan="2"> the boil or soak</td>

<td colspan="4"> periods, and the gasification rates in the table.</td><td> achieved</td><td> are</td><td> identified</td>

<td> • · • • •</td><td> • ·· ·</td><td> 15</td><td></td><td></td><td> TABLE</td><td> IV</td><td></td><td></td><td></td>

<td> •' • • •</td><td> • · • · • · •</td><td> 16</td><td colspan="3"> Comparison of Na/Ca Catalyst</td><td> with</td><td> K_oCOο On</td><td colspan="2"> Illinois Coal</td>

<td> 4</td><td> • » ···</td><td> 17</td><td></td><td> wt</td><td colspan="2"> . 7o cn Coal</td><td> Time,</td><td> Hr .</td><td rowspan="2"> Gasification. Rate-%/Hr</td>

<td colspan="2"> • • · · ·</td><td> 18</td><td> Catalyst</td><td> KZJTT</td><td> 3 3</td><td> TaS</td><td> Boil</td><td> Soak</td>

<td></td><td></td><td> 19</td><td rowspan="2"> K₉CO·, ^K2^COj</td><td> 10</td><td></td><td></td><td></td><td></td><td> 72</td>

<td></td><td></td><td> 20</td><td> 15</td><td></td><td></td><td></td><td></td><td> 100</td>

<td> • • · •</td><td> • · • • ·</td><td> 21</td><td> Na₉C0_q/Ca(0H)₉</td><td> — —</td><td> 5</td><td> 8</td><td> 0.5</td><td> 0</td><td> 47</td>

<td> • · • ·</td><td></td><td> 22</td><td> Na^COg/Ca^OH)^</td><td> --</td><td> 5</td><td> 8</td><td> 0.5</td><td> 72</td><td> 89</td>

<td> •</td><td></td><td> 23</td><td> Na-CCL/Ca(0H)₉</td><td> --</td><td> 5</td><td> 8</td><td> 1</td><td> 0</td><td> 47</td>

<td> • · •</td><td> • • ·</td><td> 24</td><td> Na₉C0n/Ca(0H)₉</td><td> --</td><td> 5</td><td> 8</td><td> 1</td><td> 1</td><td> 61</td>

<td> •</td><td> ··</td><td> 25</td><td> Na₉C0n/Ca(0H)₉</td><td> --</td><td> 5</td><td> 8</td><td> 1</td><td> 7</td><td> 64</td>

<td></td><td> •</td><td> 26</td><td> Na₉C0^/Ca(0H)₉</td><td> --</td><td> 5</td><td> 8</td><td> 1</td><td> 24</td><td> 75</td>

<td> • •</td><td> •</td><td> 27</td><td> Na^CO^/CaCOH)^</td><td> --</td><td> 5</td><td> 8</td><td> 1</td><td> 96</td><td> 81</td>

<td colspan="2"> • •····· • · ·· · • · ·</td><td> 28 29</td><td> CafOH7₂</td><td> --</td><td> 5</td><td> 2.9</td><td> (υ::</td><td> 24</td><td> 21 41</td>

(1) Weighted average rate from 0-90% carbon conversion at

1300°F. Weighted average steam/carbon is 7.5 W/W/Hr. Based on carbon actually present.

(2) Actually ion-exchanged on the coal.

- 26 These data clearly show, in particular, the pro2 motional effect of sodium on calcium. A comparison of the

Na/Ca combination with potassium carbonate, the standard catalyst, shows an activity equal to 137» potassium carbonate.

The data illustrates that soak times of 72 to 96 hours are generally necessary for maximum activity to be developed at ambient condi tions.

ε

It is apparent that various modifications can be OO

9t* made without departing the spirit and scope of the invention. S'·

10q&lt;| For example, these alkali-promoted alkaline earth catalysts, ^v4l| will also prove effective in the treating of coal derived . .. 12 carbonaceous products such as liquefaction bottoms, and with • · · • · · ” 13 other gasification agents such as hydrogen and carbon dioxide.

····

<img file="AU4277878A_D0009.tif" />

• ·

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