IE51109B1 - Hydrotreating of carbonaceous materials - Google Patents
Hydrotreating of carbonaceous materialsInfo
- Publication number
- IE51109B1 IE51109B1 IE846/81A IE84681A IE51109B1 IE 51109 B1 IE51109 B1 IE 51109B1 IE 846/81 A IE846/81 A IE 846/81A IE 84681 A IE84681 A IE 84681A IE 51109 B1 IE51109 B1 IE 51109B1
- Authority
- IE
- Ireland
- Prior art keywords
- coal
- reagent
- reaction
- temperature
- hydrogen sulfide
- Prior art date
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/10—Sulfides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
Coal, peat or wood is converted to liquid and gaseous hydrocarbons by reaction with an alkali metal sulfide, polysulfide and/or hydrosulfide, in the presence of water, steam and/or hydrogen sulfide at 50-450 DEG C.
Description
This invention relates lo a process for hydro Creeping carbonaceous materials and particularly to a process for the conversion of such materials to gaseous hydrocarbons, volatile distillates or mixtures thereof,
The application discloses further, highly beneficial developments of a process first disclosed in my United States Patent Application Serial No. 063,824 filed August 6, 1979;
United States Patent Application Serial No. 114,207 filed January 22nd, 1980; United States Patent Application Serial No. 140,604 filed April l‘)th, l()80 and UK Patent Application No. 8024908 (Serial No. 2,0'>'>,892). The specifications of the first two of the abovi-nuntioned United States Patent Applications are open to public inspection in the file of published UK Patent Application No. 8024908. Λ copy of the specification of Serial No. 140,604 accompanies the present specification and is marked Appendix A.
In my first filed U.S. Patent Application, I disclosed a meLhod for pn.paring an alkali metal reagent and a reaction based on this reagent with oxygen nitrogen and sulfur in coal.
In U.S. Patent Application Serial No. 114,207, I disclose the utilization of the method disclosed in the first filed «ipplicatioii on coals of various rank and peat and the use of water or steam in the process which may be practiced batchwise or continuously. U.S. Patent Application Serial No. 114,207 contains also a disclosure for varying the conditions so as to obiain a product mix by use of different temperatures, reagents,
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- 3 rank of coal as well as reaction stages. Further, in U.S. Patent Application Serial No. 114,207, I disclose addition of sulfur to stabilize a reagent as a less hydrolyzed polysulfide.
In U.S. Patent Application Serial No. 140,604, (on which the present application is in part, based) I disclose a number of methods for preparing reagents, the stabilization of these reagents by employing hydrogen sulfide in hydrotreating carbonaceous materials and stagewise reactions. I have now found that besides stabilization of the reagent, for coals and peat, the addition of hydrogen sulfide surprisingly provides heretofore unknown, further benefits based on the difference in the chemistry of coals or peat as distinguished from the carbonaceous materials disclosed in that application.
Parts of the subject-matter of U.S. Patent Application Serial No. 140,604 aje described and claimed in my copending UK Patent
Application No.3111869 and 8111836 filed today.
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- 4 Thia invention incorporates further developments in the inventions disclosed in the above applications and relates to conversion of coal and other carbonaceous materials to various useful component parts thereof, either, principally gaseous component parts or various proportions of gaseous and liquid component parts, including substantially liquid products uith appropriate recovery of reagent and hydrogen sulfide being provided as part of the conversion process. This invention further describes conversion of these gaseous components into other distillates; more particularly, this invention relates to the conversion of coal and other carbonaceous materials to desired conversion products thereof such as hydrocarbons in liquid or gaseous form by reacting coal in one or more stages with a particular reagent therefor, which may be the aame or different for each of the stages, but in each stuge, the reugent is in the presence of water or steam, and hydrogen sulfide. The prooess can be conducted at a low to moderate temperature and between atmospheric pressure and pressure less than 5 psig. (0.3‘j Kg/cm?').
Still further, this invention relats to conversion of coal and other carbonaceous materials to various preselected component cuts tdereof, either principally gaseous component parts, gaseous and liquid components or principally liquid components by means of specific reagents, whereby coal or peat, in the presence of thia reugent, water, steam, and hydrogen sulfide, and optionally sulfur, is converted into useful breakdown materials of coal or peat. These breakdown materials are either principally gaseous hydrocarbons obtained in u single stuge reaction or
- 5 principally liquid hydrocarbons obtained in a single stage, or tne gaseous and light liquid products (light” means low boiling point liquid), from a single stage. These products may be further reacted in one or more additional stages in presence of different reagents, steam and hydrogen sulfide to obtain liquid distillates. Ultimately, at the high temperatures, coal in tne presence of the reagent, hydrogen sulfide, and steam, causes production of some hydrogen.
It nas become increasingly evident that liquid and lo gaseous hydrocarbon sources such as petroleum and natural gas are being depleted at such rapid rate than an intensive effort is needed to meet anticipated future needs for obtaining substitute energy, feedstock, or chemical starting materials. One of the most readily available sources of
Hydrocarbon materials is coal. Heretofore, there has been no ready means, witnout extensive capital investment on economically justitiaole basis, to produce hydrocarbons from coal. Although various processes are known for conversion of coal at nign temperatures, such as high temperature i.e.
above 600°C, high pressure e.g. above 25 atmospneres coal gasification, tfjere nas been no readily available lowertemperature, low-pressure process which would readily convert coal into its component hydrocarbons.
- 6 lt baa now been found that whun coal or other curbonuceoua material is treated with a particular reagent, it can he converted in the presence of this reagent and in the presence of water and/or steam and hydrogen sulfide to various hydrocarbon fractions either principally gaseous hydrocarbon fractions of one to five carbon atoms (C, to C^), e.g., methane, ethane, ethene, etc., or principally liquid distillates. Hydrogen may also be co-produced.
Thus according to the present invention, there is provided a process for conversion of carbonaceous material to gaseous hydrocarbons or volatile distillates or mixtures of these which comprises reacting said carbonaceous material and, aa a reagent, a hydrosulfide, a 3Ulfide or a polysulfide of an alkali metal or a mixture thereof in the presence of water and hydrogen sulfide and optionally sulfur at a temperature between 50°C and 45O°C in one or more stages, wherein the temperature and reagent in euch stage may be the same or different, and recovering volatile liquid distillates and hydrocarbon gases.
At higher temperatures, more or principally gaseous hydrocarbons will be produced: moreover when using a different reagent in another reactor the gaseous hydrocarbons in the presence of steam and hydrogen 3ulfide may be further
52109
- 7 reacted to obtain different hydrocarbons such as liquid or gaseous hydrocarbons. It has also been discovered that by changing the reagent and using apparently anhydrous and eutectic mixtures of sulfides as further explained herein less gaseous hydrocarbons are produced at higher temperatures.
Further, it has been surprisingly found that hydrogen sulfide addition is considerably more beneficial than sulfur addition disclosed in my prior application because hydrogen sulfide stabilizes the reagent more effectively, and helps in conversion of the thiosulfate or the tetrathionate (and (Ze denotes two electrons).
2e) such that 2 thiosulfate ions are formed./
There is some breakdown of KHS to K2S in the presence of water. This breakdown is partial. Hence, in hydrogenating coal, both KHS and K2S should be present in the reaction.
When sulfur is added, a less hydrolyzed, and therefore, a more water-stable polysulfide e.g. potassium pentasulfide is also provided. Hydrogen sulfide not only improves the stabilization, but decreases the amount of reagent needed.
It has further been found that when mixtures of alkali sulfides are reacted these may be added in liquid state to coal to facilitate the reaction, e.g., such as mixtures of polysulfides or hydrates thereof.
When the K2S and various polysulfide species thereof, react with coal, these preferentially attack the oxygen, 25 sulfur and nitrogen present in coal in a bound form to withdraw or abstract these components of coal. As derivative hydrocarbon components are forming in the presence of reagent steam or water, and hydrogen sulfide, the bond scission of the
- a various coal constituent parts and abstraction of oxygen, nitrogen anti sultur, allow tne introduction of hydrogen from water or hyorogen sultiae and thus the formation of hydroaromatic, aromatic and shorter chain aliphatic compounds. The severity of attack can be tailored from where the product is essentially gas to where the product is essentially liquid,
Dased on the reagent (s) employed and the operating conditions.
In order to illustrate further the present invention, a drawing is presented wherein:
Figure 1 illustrates, schematically, hydrogen sulfide recovery from a gaseous value recovery train.
in tne process, once tne desired operating temperature is reached and hydrogen sulfide or steam and hydrogen sulride is being introduced into the system, an inert gas sucn as nitrogen or helium, first used to purge the system ol oxygen, may no longer be needed. Hydrogen sulfide may be introduced througn tne steam line.
In Figure 1, a scnematic illustration of a hydrogen sulfide gas recovery is provided. A reactor 22, typically at 350°C to 390°C has been charged with coal, a reagent in liquid form, water, in the form of steam, and hydrogen sulfide gas. A cooling jacket 24, surrounding the condenser 26 racilitates the cooling of the reaction gases. The initial and heavier products are recovered from condenser bottoms 27. The gaseous products are sent on to vessel 30 in which water and alkanol (typically methanol or ethanol) are held.
51108
- 9 Vessel 3ΰ receives water or alkanol from the reactor When alkanol solubilized reagent is used. The mixture of water and alcohol in vessel 30 is kept below the boiling point of the mixture and thus the lighter gases pass through such as the Οχ to C5 including hydrogen sulfide.
In vessel 31 the contents are cooled to about -35°C at which temperature liquid C4 and C5 are removed. While most of C4 ana C5 fractions are removed in vessel 31, some still are carried over to vessel 32 where these are removed at -30°C with the C3 fraction in ethanol or metnanol. A fritted glass disk 33 removes any residual foist of these components. At this state suostantially only H2S and and C2 fractions are present in the gas stream which is then introduced into vessel containing KOH and alcohol, typically etnanol or methanol in water solution. Hydrogen sulfide therein reconstitutes the reagent, which is recovered as a precipitiate, while the light fraction gases predominantly Cj_ and C2 pass. About 97% and more of H2S is recovered as a reagent component and may be reused. No H2S is vented to air. The alconol-water fraction from vessel 30 is used to repienisn the alcohol dragged out from vessel 35. However, this mixture must be cooled in heat exchanger 36.
As mentioned before, hydrogen sulfide may be introduced in the reactor as a separate stream or with steam. When it is introduced with steam it is at a point, i.e., at about 135°C and above, but at 170-190°C wnen steam is used typically hydrogen sulfide is introduced with steam. Steam is silos
- 10 not introduced into tne reaction vessel until a methanolwater mixture used for introducing the reagent has been expelled Decause tne water-methanol mixture will hold the temperature at a specific temperature range during this distillation. Hydrogen sulfide is present from the beginning of the reaction.
After the introduction of the steam or the steam and continuing hydrogen sulfide introduction, various lignites, and sub-bituminous coals, based on the inherent makeup of these, display different distillation points in the production of sizaole amounts of gaseous hydrocarbon.
The gas production increases substantially wnen 360°C is reached and wnen the final temperature is between 380°C and 450°C a very rapid gas production is encountered with some hydrogen being produced. At a temperature of 360 to 380°C carbonyl sulfide is also produced. In sub-bituminous coal e.g 4.7% Dy weight ot the total hydrocarbon gas may be carbonyl sulfide. When hydrogen sulfide is used carbonyl sulfide production appears to be suppressed, all other conditions being equal.
Without being bound to any particular theory, the, reactions, vi^ the water and hydrogen sulfide molecules, provides hydrogen to react with coal at the point where coal is being deoxygenated, desulfurized or denitrogenated.
Hence, for practice of this invention, it is necessary that oxygen be present in coal but the benefit is also gained when sulfur and nitrogen is present in coal in a form such as an organic sulfur or organic nitrogen species. Moreover,
- Η higher rank coal, such as bituminous coal, may not as readily be converted to gaseous nydrocarbons although, as explained below, it still may be done when the reaction scheme is appropriately moditied.
The present invention is further concerned preferably with lignite and sub-bituminous coal gasification, but all coals may be gasified or liquid products obtained therefrom; even wood in chip form may be gassified. Moreover, wood (cellulose, lignite, sugars, etc.) can be converted into gaseous or liquid products.
an anthracite coal of 92% carbon content wnen it is partially oxidized, can be readily converted into liquid and gaseous reaction products.
If pQtassium in coal ash is converted to hydrosulfide, no ioss of potassium hydrosulfide is experienced; and t'ne reagent balance for the reaction, on batch or continuous basis, is very favorable. Moreover, with hydrogen sulfide stabilization of tne reagent, the amount of reagent used may be decreased and excess sulfur and potassium from coal utilized, e.g., for reagent or hydrogen sulfide production.
In general, it is emphasized that sufficient amounts of sulfur, hydrogen sultitie, hyurosulfide or polysulride should De present to take up tne sulfur expelled from the reagent or to take up oxygen or sulrur in coal during deoxygenation thereby preventing the expelled sulrur from denydrogenating the coal at a tern51109
- 12 perature above 175°C. Also, the integrity of tne various reagent species must be preserved above 325°C since a temperature increase above this level will cause a slow dehydrogenation of coal by alkali metal hydroxide melt. As sulfur causes the formation of polysulfides and the alkali polysulfide is less hydrolyzed with increasing sulfur content thereof, the decomposition by steam (or other water) of the Hydrolysis product, i.e., the nydrosulfide is thereby prevented; however, hydrogen sulfide addition accomplishes best the stabilization as further explained herein.
The hydrogen sulfide generated in the addition of tne elemental sulfur to the alkanolic solution of alkali metal nydrosulfide and the reaction of the sulfur displaced by oxygen during tne conversion of coal to hydrocarbon forms is used to form additional alkali metal hydrosultide from the alkali metal hydroxide recycled in the process; but hydrogen sulride is also introduced into the reactor(s) to stabilize the reagent and therefore may be in excess ot tne amount needed in tne reaction,
Some of the potassium hyarosultide is decomposed, following Hydrolysis, into potassium hydroxide and hydrogen sulride. This potassium hydroxide provides a medium at temperatures of 360°C and higher whereby tne calcium carbonate of the limestone (in the ash content of coal) reacts with tne potassium sulfate (from the reagent residue) to form calcium sulfate and a mixture of potassium hydroxide and potassium carbonate. The potassium content of the coal ash is also extracted in tne hydroxide form.
- 13 As shown above, steam is employed at a temperature at whien tne reaction is sought to be conducted, i.e., depending on the type of coal and the decomposition levels of coal as well as the desired product. Water contained in coal is also a source of water and/or steam.
As the amount of sulfur content of the reagent is increased, i.e., from sulfur in coal, from the added elemental sulfur or from the hydrogen sulfide, the reaction temperature is lowered. For example, a reaction tenperature of 380°C ia lowered to 350°C, wnen, as an illustration, the sulfur balance is representative ot a theoretical compound produced and maintained during reaction conditions. A corollary of this phenomenon is that larger molecules are produced, for example, pentane, i.e., isopentane and pentane.
Further, rank of coal affects tne distillate makeup, the higner the rank of coal, the higher the proportion of liquid distillates under equivalent conditions, e.g., when using tne theoretical K2S3 compound at the same temperature conditions.
Of course, when the temperature is varied, the product composition changes. Moreover, as illustrated above, when tne amount of sulfur in the reagent is changed, the product composition is also changed.
Thus, based on the above, one can vary temperature, sulfur content of reagent, employment of mixtures of reagents, e.g. liquid or dissolved forms thereof, rank of coal, and u^e a recycle of alcohol absorbed distillates to obtain the desired product cut.
- 14 The above described variations are within the following prescription: temperature up to 425°C to 450°C but distillation starts at 40° to 50°C; sulfur content in reagent (e.g., for potassium) KjS but the sulfur content may go up to K2S5; sulfur or hydrogen sulfide addition; mixtures ot these reagents; liquid or solid state of reagents; contacting of a product stream with another composition of reagents, including hydrogen sulfide; and rank of coal (desirably in the lignite to bituminous coal range). When
Pq applied to antnracite, the results are less advantageous alttioujh a distillate may be obtained at +38O°C and using a reagent sucn as K254. Partial oxidation of the high rank coal also nelps.
Moreover, tne amount of recycle may also be varied.
Thus, up to about 280°C, the product composition can be forced towards a composition which is a liquid distillate of a boiling point below about 180°C. At a reaction temperature up to aoout 310°C paraffin distillates are formed wnen employing the above-described alcohol, recycle to the reaction vessel. As before, and in this recycle condition, water, i.e., steam at a temperature ot about 135°C (and above) and hydrogen sulfide must be present in order for the reaction to occur advantageously.
When starting the process at about ambient conditions (and raising tne temperature), elemental sulfur or -preferrably hydrogen sulfide is added to coal or to the reagent to obtain tne selected sulfur content for the reagent. At
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- 15 these conditions H2S formed in the system during the reaction of the sulfur and the reagent is removed from the gas stream and wash system to reconstitute the reagent as shown in Figure 1. As the temperature is being brought up, when steam is not used, any hydrogenation of coal that occurs is from the water content in coal or the reagent. At about 135°C, steam may be added if light distillates are desired. Typically, steam is added, however, at about the temperature when a hydrate of the reagent starts reforming or reconstitutes itself to a lower hydrate thereof. For potassium based reagent, steam addition temperature is selected at about 170°C.
In summary, as oxygen is removed as well as nitrogen and organic sulfur, water or, to a lesser extent, hydrogen sulfide (continually produced by contact between water and the reagents) yield hydrogen to the coal at the point where coal has been deoxygenated, desulfurized, or denitrogenated; nitrogen comes off principally as ammonia; the sulfur comes off to form an alkali (e.g. potassium) polysulfide and at lower temperatures forms a mercaptan with the alkanol. Mercaptans are absorbed in alcohol and in the KOU-alcohol solution. This overall reaction proceeds through reduction of the hydrogen sulfide gas to sulfur and water, with sub sequent reaction of the sulfur with the KOH to form the potassium thiosulfate and the potassium sulfide. The potassium sulfide can then acquire additional sulfur from hydrogen sulfide to form potassium polysulfide and are the reagents used in the reaction.
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- 16 The hydrocarbon compositions i.e., gaseous fractions, obtained at different temperature levels, may be further treated such as in another reactor with other reagent composition, that is, one higher in sulfur content and at a lower temperature from that in the first stage where the reaction temperature is 340°C to 390°C, e.g., in the next stage the temperature may be 280°C to 340°C with increasing sulfur content in tne reagent; in the third stage, the temperature may be 225°C to 280°C or 180°C to 225°C. As the uenydrogenation reaction is in competition with hydrogenation reaction, with increasing sulfur content in reagent and tne presence or sulfur, this causes dehydrogenation of tne product stream tnat is initially gaseous. This stream can then be treated to obtain the desired product composition,
i.e., API Number, for a preselected product. In other words the initial gaseous products are reformed into products as dictated by tne demand.
As mentioned before, the above process has been improved uy the addition of hydrogen sulfide to the reagent during tne coal or coal product hydrogenation stage, i.e., the alkali metal sulfides, mixtures of sulfides such as in their.
✓ hydrated form etc. The hydrogen sulfide addition, apparently, xeeps tne selected reagent in a stable state so tnat a reaction once initiated with that particular reagent or reagent mixture will produce, with few variations, from the same source material, when keeping all other conditions constant, substantially the same products or mixtures of
- 17 products. Consequently, proper stagewise arrangement' of reagents, tneir compositions for each of the stages, temperature conditions and water addition will be further improved by the nydrogen sulfide addition to the above described process so that a greater range of products, selected product mixture and a more precise degree of hydrogenation (including dehydrogenation of a product stream(s), wnen desired), are now possible.
The appropriate alkali metal sulfides, mixtures of the sultides, and mixtures of the foregoing sulfide(s) nyurates with nydrogen sulfide present give the desired reagent stability, and tne selected product. When the reagent is thus properly maintained in the active reagent state by the addition of hydrogen sulfide, the benefits are:
reduced amount of reagent, better yields, and better product control.
The reasons for the hydrogen sulfide addition follow from the illustrated reactions.
1. 4KOH + 4H2S --- 4KHS + 4H2D
When coal derived sulfur is present then
2. 4S + (5 KOH-* K2S2O3 + 2K2S + 3H2O in turn J
3. K2S2O3 + 3H2S-ft. K2S5 + 3H20 tne decomposition of K2S2 is as follows:
4. 4K2S2 + 8H2O -* 4K0H + 4KHS + 4S + 4H20
Hence, if H2S is present, KOH is converted to KHS and if any KOH forms the thiosulfate, then the thiosulfate is converted to K2S5·
1103
-ρ.
- IB Further reactions are as follows:
. K2S5 -, K2S4 + S (above 300°C)
6. K2S4 -* K2S3 + S (above 460°C)
7. KhS + K2S + 3H2O -j, 3K0H + 2H2S
Θ. K2S + H2O -ο KOH + KHS
9. KHS + H20 --► H2S + KOH
. KHS + KOH -J, K2S · xH2O (x can be, e.g., 2, 5, etc., depending on temperature). Hence, enough H2S snould be present to keep the reactions, by mass action, in a state, where the reagent is stable, i.e., sulfur is taken up either when freed from coal or from the reagent, and hydrogen sulfide keeps the reagent from hydrolyzing. Moreover, tne thiosulfate generated by the oxygen present in coal is regenerated during the reaction to tne desired K2S3 sulfate. Thus, the reagent is kept in the desired nydrolysis level by H2S.
Of the various reagents, tne following are preferred .
because of stability and sulfur acquisition ability, KHS,
NatiS, K2S, K2S2, K2S3; an these, the order of preference is as follows: K2S2, K2S and then K2S3. The other sulfides display instability at their melting points, e.g., Na2S2 at
445°C, Na2S4 at 275°C; or give off sulfur at 760 mm, e.g., ✓
K2S5 at 300°C yields K2S4 + S; K2S4 at 460°C yields K2S3 +
S; anu K2S3 yields K2S2 + S at 780°C.
Melting points of tne alkali sulfides illustrated above are as follows: for K2S at 948°C; K2S2 at 470°C; K2S3 at 279°C (solidification point); K2S4 at 145°C; K2S5 at 206°C;
- 19 K2Sg at 190°C. Melting points foe mixtures of the sulfides (pure or eutectic mixtures) are as follows: for K2S - K2S2 it is 350°C; for K2S2 - K2S3 it is 225°C; for K2S3 - K2S4 it is. about 11Q°C; for K2S4 “ K2S5 is 183°C. Based on the various illustrations above, appropriate temperature conditions are selected as dictated by decomposition and/or melting point characteristics so as to allow the use of a solid reagent, or a stable liquid reagent such as for coating the coal. Of course, the various hydrates of the alkali sulfides nave various melting and/or decomposition points which, of course, also holds true for the eutectic mixtures. These temperature points may be readily established tnermographically as it is' well known to those skilled in the art.
The coal conversion process proceeds without a reagent instability, i.e., alkali sulfide hydrate instability, because hydrogenation of coal is preferrential to reagent decomposition and addition of hydrogen sulfide aids in the stabilization of the reagent. Moreover, while the reaction witn coal will proceed with adequate amount of reagent present, the addition of hydrogen sulfide also decreases the amount of the ’reagent necessary because the reagent is in a more stable form, hence, tne process is also improved on tnat basis. The use of hydrogen sulfide doubles at least the product recovery, all other conditions being the same.
In general, the hydrogen sulfide addition will be on a space time velocity basis and will be typically in a range from 40 to 120 ml/min/gal (about 10 ml/min/liter to 30
- 20 ml/min/liter) of reactor space with about 20 ml/min/liter being typical. Expressed on another basis, one half gram mole, and less of H2S is added for 1000 ml of water removed by the hydrogenation reaction. In describing the various sulfides and their decomposition temperatures including the reactions, my U.S. Patent 4,210,526 issued July 1, 1980 is relevant.
At peak operating temperature herein, e.g., 450°C,
K2S5 will yield sulfur, (which is a useful phenomenon as has been explained herein in connection with dehydrogenation of further process streams). Inasmuch as the decomposition temperatutes are lowered at lower pressures, the coal conversion at atmospheric pressure is entirely feasible, although some benefit is gained by operating at elevated pressures, e.g. above 5 atm., the added cost and other expenditures make this merely a less desired method of operating the coal conversion process. Hence, for practical purposes the variation of the pressure conditions can be from about atmosphere to about 5 atmospheres, but the ambient atmospheric pressure is preferred.
Although the reaction mass of coal and reagent may be appropriately §tirred, it is best to precoat coal with a reagent in the absence of oxygen, as oxygen has a tendency to destroy the reagent.
For this reason, it has also been found useful to employ a liquid or a dissolved reagent. Liquid, yet stable reagents may be employed for coating coal at or above the
- 21 appropriate melting point ot the selected reagent or the liquid eutectic mixture of these.
For example, a mixture of K2S3 - K2S,j maY be used above 110°C in a liquid state to coat coal. As solvent for the above reagent, glycerol has been found to be very useful. Any solvent which will dissolve the sulfides and will not affect their activity may be employed. About 88 grams of KHS is solubilized to make a total of 200 ml glycerol solution. When the mixture is heated up to 175°C (glycerol will decompose above 190°C), H2O is driven off from the dissolved KHS mixture and the mixture will then contain K2iJ • xii20. Oxygen is excluded also from this reaction mixture. This mixture can then be readily used tor coating coal and tnus serve as a reagent.
Inasmuch as the severity of the attack on sulfur, nitrogen and oxygen on coal is a function of the reactant composition and tne amount thereof, the following points may be mentioned. Gaseous conversion of coal is accomplished when degradation, of coal, i.e., reagent attack thereon is most severe. Less severe degradation produces lighter distillates. At 175°C, sulfur starts to dehydrogenate coal and therefor «> presence of sulfur is not desired for coal conversion. Therefore, a stable reagent is employed at those conditions. However, for reformation, i.e., dehydrogenation and reaction of dehydrogenated species with each other, that reaction is important as it allows preselected obtention of liquids ot different boiling points (or preselected API
1109
- 22 number). Ot course, coal derived gases are an ideal feedstock for reforming hydrocarbons. As mentioned above, tne rank of coal also affects the reactions. For poorer coal, to achieve least degradation high sulfur content reagents are used. For more complete gassification, the amount of sulfur in the reagent is decreased, e.g., K2S is used, whereas K2S5 is used for less severe attack. This is especially true for peat when it was reacted with K2S5, it gave essentially naphthalene.
The above illustration of the process as well as the invention herein is described by reference to the examples whicn are not intended as a limitation of the invention, but rather as an illustration of an embodiment thereof.
EXAMPLE 1
A reaction vessel of, 1 gallon capacity, is equiped witn a steam line, a heating-cooling means, a thermocouple, stirrer, and an exit conduit for the reaction gases. Hydrogen sulfide is added with steam and it may also be added separately. The products are recovered in a condenser appropriately cooled while the gases are collected as previously illustrated in the Figures herein.
To 800 grams- ot Kentucky #9 coal held under a helium gas blanket, in the described vessel, was added a liquid mixture of K2S3 and K2S · 51(20. The added amount of the reagent mixture was 2 moles, i.e., one mole of each. One mole was K2Sj obtained from a mixture of K2S and K2S5 in a water solution adjusted to an empirical formula K2S3, Further, 4
- 23 grams of KOH was added, which serves to drive off NH3 at process conditions. The mixture was stirred so as to coat tne coal particles with the reagent.
After this, steam was added together with H2S at 80 ml/min at a temperature of 50°C. The reaction was exothermic and was not allowed to rise above 450°C but kept as much as possible at about 350°C to 390°C. Steam was added at 135°C at a rate equivalent to hydrocarbon withdrawal or at 130% thereof, the recovered product was a clear amber red solution, wnicn, when treated under same conditions with 19 gr of KHS, up to 240°C, completely distilled to a water clear hydrocarbon liquid distillate (almost water clear hydrocarbon) and of a water like viscosity. A total of 324 ml of distillate was recovered including 12 liters (N.T.P) of gas during the first reaction stage. The product analyzed as follows:
Soiling Point Range 180°F initial boling point and
% - 460°F (238°C) 20% - 479°F (248°C) 30% - 486°F (252°C) 40% - 492°? (256°C) 50% - 500°F (26O°C) 60% - 508°F (264°C) 70% - 522°F (272°C) 80% - 538°F (281°C) 90% - 562°F (294°C) 95% - 592°F (311°C) 90.6% - 632°F (333°C)
- 24 EXAMPLE 2
In order to illustrate the efficacy of H2S addition, 110 grams of bituminous coal (on a dry ashless basis), was reacted with solid NaHS (technical grade), or KHS (in water solution), in a reaction vessel as previously described, with addition of H2S at 80 ml/min and 200 ml helium. Steam was added at a temperature above 137°C at a rate from equal to 130% of hydrocarbon condensate removal. Addition of KOH, suppresses ammonia reactions within reactor and expels ammonia. The reaction becomes exothermic at 390°C. 252 liters of gas and 70 ml of liquid hydrocarbon condensate was obtained before the reaction run off exothermically above 390°C.
When runs were made on lignite with and without H2S addition, the yields were more than doubled for the run with n2S addition. Another reagent was as illustrated in Example 1. The reaction also became exothermic above 390°C.
About 3 moles of H2S per mole of K2S2O3 formed is necessary. Further, about 48 grams of coal based oxygen is used up when one mole of K2S2O3 is formed.
About 42% of wood is oxygen and about 2% of anthracite is oxygen. Between these limits H2S is added based on the above reaction as a maximum, as there are other competing reactions. The above is a rough indication of the amount of h25 needed but in practice lesser amounts are used, e.g. due to the principal side reaction of diatomic hydrogen uniting with oxygen to form water.
When KHS and/or NaHS are used these produce copious
513.0
- 25 amounts of gas, and the reaction becomes exothermic above 390°C. K2S2 5H2O plus K2S (empirical, based on equal molar quantities of K2S · 5H2O and K2S3) produces little gas and con siderable amounts of liquid condensate, from the same source material, but the reaction is exothermic from inception,
i.e. about 50°C and the reaction seems to maintain itself at 390°C with little heat input. K2S2 (derived from a melt of K2S · 5H2O plus sulfur) mixed with an equal quantity of K2S (derived from hot KOH aqueous solution plus sulfur in a ratio of 6K0H + 4S, as a reagent, produces liquid distillate and gas. The reaction becomes exothermic at 240°C when used on the same source material. In all three instances the source material was -200 mesh Kentucky No. 9 bituminous coal and the reaction condition were otherwise identical, i.e. steam,
H2S, and helium were used as previously illustrated. The foregoing shows the possibilities of obtaining gas, gas and distillates, and substantially distillates, and moreover, shows the highly advantageous nature of the exothermic reactions. During these exothermic reactions, negligible
2o amounts of CO and C02 were formed. In the gas streams, after scrubbing, hydrogen sulfide was nondetectable. Apparently, no COS was formed.
The· above is further illustrated by the following example.
9
- 20 EXAMPLE 3
The following reagent was employed on Kentucky #9 coal:
(1) K2S ·51120 + S (2) theoretically: K2S 2 -} (K2S + K2S5) Two layer (4S) x (0.83) + 6K0H (aqueous) -> of each (1) and (2) above, one half mole of each was used
when making up the reagent.
The coal analysis is as follows: Untreated Table I Kentucky #9 Coal: Ultimate of Ash %As Kecd % Dry Moisture 2.58 54.15» Λ £ 3 □ . 52 8.75 ai2o3 24.79% Volatile 35.36 36.90 Fe2O3 13.72% Fixed Carbon 53.54 54.95 TiO2 1.69% BufIfur 2.62 2.69 CaO 0.72% Btu/lb 12952 13295 MgO 0.85% Btu/lb minus ash fraction 14509 Na2O 0.35% Carbon 71.60 73.50 K2O 2.44% Hydrogen 4.87 5.00 Li20 135 PPM Nitrogen 1.59 L.63 P2°5 SO 4 0.38% Oxygen 8.22 8.43 0.77% Chlorides 0.22 0.23
**__
- 21 51109
Table II
Product Recovered After Reaction:
Degrees API @60°F (16°C) Specific Gravity @60°F(16°C) 16.9 0.9530 Sulfur % BTU per pound BTU Per gallon Carbon Hydrogen Sulfur Nitrogen Oxygen Distillation Results 0.17 18145 144089 88.62 10.19 0.17 0.19 0.83 .... ** Table III of Product Shown in TABLE Initial Boiling Point 342°F (172°C) 5% Recovery 440°F (227°C) 10% Recovery 4 86 °F (252°C) 20% Recovery 492°F (256°C) 30% Recovery 510°F (266°C) 40% Recovery 528°F (276°C) 50% Recovery 53 8 °F (281°C) 60% Recovery 544°F (284°C) 70% Recovery 57 8 °F (3O3°C) 80% Recovery 610°F (321°C) 90% Recovery 670°F (354°C) 95% Recovery 710 °F (376°C) End Point 710 °F (376°C) % Recovered % Residue 96.0 3.7
% Loss
0.3
110 9
- 2» Table IV
Analysis of 0-50% Distillate Product:
Degrees API y60°F (16°C) 20.9 Specific Gravity t)60°F flC°C) 0.9287 Sulfur % 0.15 BTU per pound 18691 BTU per gallon 144519 Carbon 02.17 Hydrogen 10*00 Sulfur 0*15 Nitrogen 0*18 Oxygen 2.42
Table V
Analysis of 50% to End Point Distillate
Degrees API @60°F (16°C) 16.4
Specific Gravity @60°F Q6°P) 0.9568 Sulfur % 0-14
BTU per pound 18550
BTU Per gallon 147788
Carbon 90.45%
Hydrogen 8.47%
Sulfur 0.14%
Nitrogen 0.31%
Oxygen 0.63% __ Λ it — —
S1109
- 29 The above Example 3 illustrates typical upgrading of coal and conversion of same to liquid products.
It has been demonstrated above, that a readily available source of a great variety of hydrocarbons may be realized from coal by a very flexible process carried out at low temperature, low pressure and, under certain conditions, exothermically.
In the above examples all percentages are by weight.
Claims (2)
- CLAIMS 1. A process for conversion of carbonaceous material to gaseous hydrocarbons or volatile distillutea or mixtures of these which comprises reacting said carbonaceous material and, as a reagent, a hydrosulfide, a 3ulfide or a polysulfide of on alkali metal, or a mixture thereof in the presence of water and hydrogen sulfide and optionully sulfur at a temperature between 50°C and 45O°C in one or more stages wherein the temperuture and reagent in euch stage may b.· the aame or different and recovering volatile liquid distillates ani hydrocarbon gases.
- 2. A process according to Claim 1, wherein suid carbonaceous material comprises coal, peat or wood. •i. A proc .-.is for conversion of coal, peat, or wood to gaseous hydrocarbons or volatile distillates or mixtures of these by reacting coal, peat or wood and us a reagent, an alkanolic solution of an alkali meta] hydrosulfide, a 3. Ulfide a polysulfide or mixtures thereof, ut a temperature of 50°C and above, in the presence of water as water of hyiration, water, or steam, with hydrogen sulfide being present, continuing said reaction in one or more stages at a temperature up tp 45O°C with the temperature and reagent being the same or different in each stage, and further conducting said reaction at exothermic conditions, at least in the first stage and recovering volatile liquid distillates and hydrocarbon ga3es. 51199 - 31 4. Λ process a3 claimed in Cluim 3, wherein the reagent is formed by adding elemental sulfur to an alkanolic solution of said alkali metal hydroaulfide. 5. Λ process as claimed in any preceding claim, wherein said 5 alkali metal hydrosulfide is potassium hydro3ulfide. 6. A process a3 claimed in any of Claims 1 to 4, wherein said alkali metal sulfide is sodium hydro3u'lfide. 7. A process ns claimed in any of Claims 1 to 4, wherein said alkali metal hydrosullidu is a mixture of rubidium, potassium, and sodium hydrosu Ll’ides und sulfides. 8. A process according to any preceding claim, wherein hydrogen sulfide is recovered. 9. A process according to any of Claims 2 to 8, wherein the coal is lignite coal. 15 10. A process according to any of Claims 1 to 0, wherein the coal is sub-lignite. 11. A proe- ss acording to any of Claims 2 to 8, wherein the coal is anthracite coal, partially oxidizing anthracite coal, bituminous or sub-bituminous coal. 20 12. A process according to any of Claims 1 to 8, wherein peat is reacted. 13. A process a3 iaimed in any one of Claims 1 to 4, wherein the alkali metal is potussium. 14· A process according to any preceding claim, wherein part of 25 the distillate Ϊ3 treated in another stage with a ieag.int with higher sulfur content in tho presence of uydrogen sulfide. - 52 15. A process according to any preceding claim, wherein the [•«action i.e conducted nt a temperature between 1'55°C and 45O°C. 1b. A process as defined in Claim 15, wherein the reaction ia conducted at a temperature between 170°C and 580°C. 5 17. A continuous process for conversion of coal, peat, or wood to gaseous hydrocurbona and volatile distillates which comprises continuously introducing the coal, peat or wood couted with a reagent, into a reaction zone, said zone being maintained above 50°C and up to 45O°C, 3aid coal, peat or wood being treated to expel atmospheric 10. Oxygen, wherein an a reagent, 13 used a hydrosulfide, a sulfide or polysulfide of ari alkali metal, or mixed alkali metals and mixtures of hydrosulfides, sulfides and polysulfides thereof so as to coat said coal, peat or wood; introducing hydrogen 3ulfide and water or steam, in at leust 15 one reaction zone at a temperature between 160°C and up to 45O°C; reacting continuously in at least one zone at a predetermined temperature and a predetermined reagent composition, said coal, peat or wood or decomposition product thereof with the reagent in the presence of said introduced hydrogen sulfide and water or steam the 20 reaction temperature and the sulfur content hydrate form and melting point of the ruagent being selected so as to produce a desired gaseous product or volati1« distillate; recovering volatile and/or gaseous products from said reaction zone; recovering hydrogen sulfide from said reaction zone; 5110S - 'ί ί recovering coal, peat or wood nah from said reaction zone; recovering unreaeted reugunt in said coal, pent or wood aali and alkali metal valuoa aa alkuli metal hydroxides; reacting aaid alkali metal hydroxidea with at leaat part of hydrogen sulfide given off during aaid reaction and reconstituting said reagent, and recovering hydrogen sulfide for supplying the same to the reaction; introducing a sufficient amount of 3aid reconstituted reagent in aaid reaction zone so aa to continue said reaction of coal, peat or wood or decomposition products thereof with said reagent. 18. A process as claimed in Claim 17, wherein a first reaction zone is maintained at a set temperature selected so as to promote the production of gaseous hydrocarbons. 19. A process as claimed in Claim 17, wherein a reaction zone is maintained at a temperature suitable for recovery of a predetermined liquid hydrocarbon cut. 20. A process as claimed in any one of Claims 17 to 19, wherein the gaseous hydrocarbon ia treated in a second reaction zone with a different reagent to produce liquid distillates. 21. A process as claimed in any one of Claims 17 to 20, wherein the coal which is reacted is lignite coal. 22. A process as claimed in any one of Claims 17 to 10, wherein anthracite coal or oxidized anthracite coal is reacted with said regent. - 34 23- A process us claimed in any one of Claims 17 to 22, wherein potassium sulfide, potassium polysulfide, a potassium hydrosulfide or hydrates thereof, or a mixture of same is used as a reagent. 24- A process as claimed in any one of Claims 17 to 23, wherein said reaction is exothermic in a first reaction zone. 25. A process aa claimed in any one of Claims 17 to 24, whorein the temperature in said reaction zone is increased in stages between 170°C to 45O°C. 26. A process as claimed in any one of Claims 17 to 25, wherein said hydrocarbon product, in liquid or gaseous form, 13 treated in separate stages with reugent with increasing sulfur content at discrete, deen-as trig temperature ranges between 400°C but at a temperature above 1(J(J°C. 27. A process us cluimed in Claim 26, wherein the gaseous hydrocarbon is scrubbed in an alkali metal hydroxide solution thereby removing hydrogen sulfide from said gaseous hydrocarbon as a reaction product with said alkali metal and further recovering said reagent for recycle of same. 2U. A process us claimed in any one of Claims 17 to 22, wherein said reugent has a theoretical composition K^S^, on the basis of material balance. 29· A process according to any one of Claims 1, 3 and 17 and substantially hereinbefore described. 30. Caseous hydrocarbons or volatile distillates whenever produced by a process according to any preceding claim.
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US14060480A | 1980-04-15 | 1980-04-15 | |
US06/220,021 US4366044A (en) | 1979-08-06 | 1981-01-05 | Process for conversion of coal to hydrocarbon and other values |
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US1300816A (en) * | 1915-09-11 | 1919-04-15 | Standard Oil Co | Process of desulfurizing petroleum-oils. |
US1413005A (en) * | 1919-03-13 | 1922-04-18 | Standard Oil Co | Process of desulphurizing petroleum oils |
US1729943A (en) * | 1921-06-14 | 1929-10-01 | Firm Of Internationale Bergin | Treatment by pressure and heat of heavy mineral oils and carbon material |
US1904586A (en) * | 1926-12-22 | 1933-04-18 | Ig Farbenindustrie Ag | Conversion of carbonaceous solids into valuable liquid products |
US1938672A (en) * | 1929-07-05 | 1933-12-12 | Standard Oil Co | Desulphurizing hydrocarbon oils |
US1974724A (en) * | 1931-03-23 | 1934-09-25 | Shell Dev | Process for refining mineral oils |
US2145657A (en) * | 1936-12-30 | 1939-01-31 | Universal Oil Prod Co | Process for the hydrogenation of hydrocarbon oils |
US2551579A (en) * | 1944-06-30 | 1951-05-08 | Berl Walter George | Production of valuable organic compounds from plant material |
US2950245A (en) * | 1958-03-24 | 1960-08-23 | Alfred M Thomsen | Method of processing mineral oils with alkali metals or their compounds |
NL129112C (en) * | 1960-03-09 | |||
US3185641A (en) * | 1961-12-15 | 1965-05-25 | Continental Oil Co | Removal of elemental sulfur from hydrocarbons |
US3252774A (en) * | 1962-06-11 | 1966-05-24 | Pullman Inc | Production of hydrogen-containing gases |
US3368875A (en) * | 1965-02-01 | 1968-02-13 | Union Oil Co | Apparatus for the treatment of mineral oils |
US3382168A (en) * | 1965-03-01 | 1968-05-07 | Standard Oil Co | Process for purifying lubricating oils by hydrogenation |
US3354081A (en) * | 1965-09-01 | 1967-11-21 | Exxon Research Engineering Co | Process for desulfurization employing k2s |
US3483119A (en) * | 1966-03-02 | 1969-12-09 | Exxon Research Engineering Co | Hydrofining processing technique for improving the color properties of middle distillates |
US3553279A (en) * | 1968-03-29 | 1971-01-05 | Texas Instruments Inc | Method of producing ethylene |
US3565792A (en) * | 1968-06-07 | 1971-02-23 | Frank B Haskett | Cyclic process for desulfurizing crude petroleum fractions with sodium |
US3617529A (en) * | 1969-03-17 | 1971-11-02 | Shell Oil Co | Removal of elemental sulfur contaminants from petroleum oils |
US3663431A (en) * | 1969-10-15 | 1972-05-16 | Union Oil Co | Two-phase hydrocarbon conversion system |
US3745109A (en) * | 1970-10-01 | 1973-07-10 | North American Rockwell | Hydrocarbon conversion process |
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US3788978A (en) * | 1972-05-24 | 1974-01-29 | Exxon Research Engineering Co | Process for the desulfurization of petroleum oil stocks |
US3787315A (en) * | 1972-06-01 | 1974-01-22 | Exxon Research Engineering Co | Alkali metal desulfurization process for petroleum oil stocks using low pressure hydrogen |
US3926775A (en) * | 1973-11-01 | 1975-12-16 | Wilburn C Schroeder | Hydrogenation of coal |
US3960513A (en) * | 1974-03-29 | 1976-06-01 | Kennecott Copper Corporation | Method for removal of sulfur from coal |
US3944480A (en) * | 1974-03-29 | 1976-03-16 | Schroeder Wilburn C | Production of oil and high Btu gas from coal |
US3933475A (en) * | 1974-05-06 | 1976-01-20 | Rollan Swanson | Extraction of copper from copper sulfides |
US3957503A (en) * | 1974-05-06 | 1976-05-18 | Rollan Swanson | Extraction of zinc and lead from their sulfides |
US4003823A (en) * | 1975-04-28 | 1977-01-18 | Exxon Research And Engineering Company | Combined desulfurization and hydroconversion with alkali metal hydroxides |
US4007109A (en) * | 1975-04-28 | 1977-02-08 | Exxon Research And Engineering Company | Combined desulfurization and hydroconversion with alkali metal oxides |
US4018572A (en) * | 1975-06-23 | 1977-04-19 | Rollan Swanson | Desulfurization of fossil fuels |
US4078917A (en) * | 1976-01-26 | 1978-03-14 | Rollan Swanson | Extraction of antimony trioxide from antimony sulfide ore |
US4030893A (en) * | 1976-05-20 | 1977-06-21 | The Keller Corporation | Method of preparing low-sulfur, low-ash fuel |
US4119528A (en) * | 1977-08-01 | 1978-10-10 | Exxon Research & Engineering Co. | Hydroconversion of residua with potassium sulfide |
US4155717A (en) * | 1978-01-03 | 1979-05-22 | Atlantic Richfield Company | Process for removing sulfur from coal employing aqueous solutions of sulfites and bisulfites |
US4147611A (en) * | 1978-02-13 | 1979-04-03 | Imperial Oil Enterprises Ltd. | Regeneration of alkali metal sulfides from alkali metal hydrosulfides |
US4147612A (en) * | 1978-02-13 | 1979-04-03 | Imperial Oil Enterprises Ltd. | Regeneration of alkali metal sulfides from alkali metal hydrosulfides |
US4210526A (en) * | 1978-04-20 | 1980-07-01 | Rollan Swanson | Desulfurizing fossil fuels |
US4160721A (en) * | 1978-04-20 | 1979-07-10 | Rollan Swanson | De-sulfurization of petroleum residues using melt of alkali metal sulfide hydrates or hydroxide hydrates |
AU537070B2 (en) * | 1979-08-06 | 1984-06-07 | Swanson, Rollan Dr. | Converting coal to gaseous hydrocarbons and volatile distillates |
US4248693A (en) * | 1979-11-15 | 1981-02-03 | Rollan Swanson | Process for recovering hydrocarbons and other values from tar sands |
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