JPS58118890A - Coal hydrogenation producing hydrocarbon liquid and gas product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a hydrocarbon liquid product in which unconverted coal and ash solids are removed from a coal-derived liquid fraction by acid precipitation to produce a low sulfur and low ash hydrocarbon liquid product. and relating to a coal hydrogenation process for producing gaseous products.

Prior art Usually, H-:y-le Grosse X (H-coax”
A typical process step in a coal hydrogenation and liquefaction process such as a hydroclone process for solid-liquid separation produces a relatively low ash residue recycle stream that is used to make coal feed to the reactor. Includes equipment.

However, a problem with controlling the Hydraulone apparatus is that it significantly reduces its ability to perform solid-liquid separations. In industrial scale coal liquefaction processes,
This necessitates the use of an undesirable large number of individual hydroclone devices in conjunction with double line connected piping systems.

Additionally, the small size, high flow rates, and handling of polishing slurry result in significant wear on the hydroclone, which often requires replacement.

il[tA! In the case of coal hydrogenation processes such as the H-coal Grosseshueller fuel product format using ffJIJJ, the process also uses KFi non-distillable oils, yet technically combustible fuels for electrical applications. Low ash net production Q'y (
An effective homoliquid separation system using a solvent precipitation process to produce low ash nat product) can be included. However, the homogeneity of coal liquids using such solvent precipitation processes to produce boiler fuels is extremely difficult. Solvent precipitation treatment of coal solids appears to be due to the addition of solvent-poor hydrocarbon liquids to heavy coal-conducting liquids to precipitate asphaltenes and glare 7-artenes.

Asphaltene t'i ash and solid particles of unconverted coal are melted to co-precipitate the solids resulting in a highly viscous downstream material containing a large amount of high molecular weight oil. Using solvent oil from an external source. The above solvent precipitation process for coal-derived liquids is described in U.S. Pat. Nos. 8,791,956 and 8,982'266.

However, in the coal water billing method, it does not occur by itself.
So-called foreign resistance fI! I agent liquid (extranao
ug, antisolvent 1quid) requires complete separation and recovery, which is extremely expensive.

It is also known in the prior art to precipitate the heavy fractions by treatment with petroleum distillate and coal-derived liquid Yr acid at near ambient temperature. For example, US Pat. No. 7, US Patent No. 7, describes treating asphalt material in oil with sulfuric acid and an aromatic material to solidify the asphalt material. Also, US Patent No. 2
No. 209,128 describes mixing coal tar oil with paraffinic hydrocarbons and dilute acids and allowing the precipitate to settle out to obtain clean diesel fuel. Additionally, U.S. Pat. No. 8,084,118 discloses adding a hydrocarbon precipitant oil and an acid coagulant such as sulfuric acid to a tube at a relatively low temperature to obtain a supernatant ash-free liquid product, and adding the acid and carbon to the tube at a relatively low temperature. A method for purifying a coal-derived liquid is described that yields a soft sludge containing residue.

The present invention improves upon the prior art for coal hydrogenation processes and purification by precipitating the Ruasphaltene component of the recycled coal liquid, rather than using acid precipitation as a purification step in the product using inorganic acids. It is. Replacing the acid precipitation process with a hydroclone same liquid separation system in a conventional H-coal process arrangement;
DISCLOSURE OF THE INVENTION The present invention uses the overflow liquid product as a circulating oil for slurrying feed coal.The present invention discloses the use of an inorganic acid in a coal-derived liquid to remove glare asphaltenes, unconverted coal, and ash solids. [A coal hydrogenation process that produces hydrocarbon liquid and gaseous products that are precipitated to produce a clean oil product. Since the glare 7-artene contained in the heavy liquid part is a salt of nitrogen base and phenolic acid, these salts are removed and a strong inorganic acid such as hydrochloric acid is added to the heavy coal-derived liquid. The O supernatant overflow material, which was determined to precipitate basic components (BA810 moiety), was recycled to the catalytic reaction zone for further reaction, and the precipitated material was removed for further processing to reduce the liquid product yield. increase.

7M In particular, in a coal liquefaction process such as the H-coal process used in the present invention, about 446.7°C (about 8
Heavy coal that normally boils above 00'F) and contains oil, asphaltone, pre-asphalt, unreacted coal and ash solids - derived liquid portion t - treated with an inorganic acid such as chloride water 1 O acid is added to the slurry liquid part of the coal refining process at 204.4~815.6℃ (400~1300℃).
"F) at a temperature in the range of Destruction of altenes reduces the viscosity of the residual liquid [t- Precipitation of the basic part occurs during bath salt precipitation and co-precipitates the ash and unconverted coal of the solids. The liquid stream is low in solids, low in nitrogen to remove bases, and has a lower viscosity, making this material more desirable for reaction zones than those produced by hydrochloric solid-liquid separation systems. A recirculated 3iI stream is obtained to achieve a more desirable product yield from the reactor. To this end, a hydrochloric subsystem is typically used to remove solids from the liquid recycled to the reactor through an acid treatment and precipitation step. The preferred process arrangement is to recirculate the feed coal from the acid precipitation step for use as a slurry.The components of the recycled liquid stream are recycled to the acid precipitation tank. The feed coal is t-7 laundered and some of the distillate is recycled.The sedimentation tank residue material can be taken out and passed through the vacuum distillation process, and before the coker, a solid separation system tM precipitation process is used. 0 to recover a clean additional hydrocarbon liquid product. If desired, the settler residue material can also be used as a feed to a hydrogen production plant.
It can be used as a feed to a gasification plant or as a boiler fuel with on-side flue gas cleaning.

The acid used in the present invention must be a strong inorganic acid, such as hydrochloric acid (HRI), phosphonic acid (H, PO4
) and plainsted acids such as sulfuric acid (H, So, ), and boron trifluoride (BF, ) and chloride 7 /I/
The acid is added to the liquid in an amount sufficient to precipitate the glare asphaltene material. Also, 1!l is added to the liquid in a liquid state or through the coal-derived liquid. It can be added in a gaseous state.

The advantage of this acid precipitation-separation step is that it is a potentially simple and inexpensive process step with low utility requirements for hydroclons and solvent precipitation solid-liquid separation equipment. It also has the advantage of providing a hydrocarbon liquid product with low viscosity and low sulfur, which is a desirable fuel product.

Next, preferred embodiments of the present invention will be described with reference to the accompanying drawings.As shown in the accompanying drawings, the present invention will be described with reference to a boiling catalyst bed. In the accompanying drawings, bituminous or semi-bituminous coal is fed through line 10 and is first sent to a separation device 12 . In this equipment, the coal is dried of almost all surface water, ground to the desired size, and sieved for uniformity. In this case, the coal preferably has a total particle size of about 50 to 875 mesh (U, S, sieve series).

The fine coal is sent via line 1δ to slurry tank 14 where it is mixed with the slurry oil produced in the process from line 15. To obtain a slurry that can be effectively transported, the pulverized coal is mixed with at least about an equal weight of slurry oil. The generated coal-oil slurry is pumped to 85.15~851.54cm/cm" (50o
-500o psi) and then passed through heater 1B to heat the slurry to 815.6-426.7°C.
This heated coal-oil slurry is heated to a temperature in the range of (600-800”F) and is sent to reactor go via line 19i along with recycled hydrogen from line 17.
In order to supply the required fresh make-up water from line 88a, the coal-oil slurry and hydrogen-containing mixture is passed through flow distributor 21 at a flow rate, temperature and pressure to achieve the desired hydrogenation. The catalyst bed 22 passed uniformly from the bottom of the reactor upwards through the reactor 20 having the catalyst bed 2z is made of Alnona,! O may be formed from the group of cobalt, iron, molybdenum, nickel, tin or other hydrocarbon hydrogenation catalyst metals well known in the art, supported on a support selected from the group of gnesia, silica or similar materials; The granular water atomization catalyst is transferred from line 28 to reactor 20 at a rate of about 0.046 to 0.909 yen (about 0.1 to
2.0 bond) of the catalyst, which can be added at a rate of 0.0 bond), and the solid particle bed contains at least 10 g of its fixed volume, usually from 20 g. By flowing the liquid and gaseous materials cocurrently upward through the 100 cm expanding reactor, the solid particles are caused to undergo random boiling motion within the reactor due to the upward flow. What are the characteristics of an ebullated bed at a certain rate of volumetric expansion? Fine and light particles? The catalyst bed can be passed upwards, so that the contact particles that make up the boiling bed can be retained in the reactor, and thin, light materials can be passed through the reactor.0 Catalyst upper limit 2jla is the upper limit of boiling to prevent the contact particles from rising any further.

In general, the contact material is completely sealed with a fixed catalyst! Approximately 0.400~
8.20417cm” (approximately 25-200 tb/ft
), and the liquid flow rate is within the horizontal cross-sectional area of the reactor.
09871"(1ft") approximately 0.815~7.5
70/,/sec (approximately 6-1 g O gallons/min) and the expansion volume of the ebullated bed is usually no more than twice the volume of the fixed catalyst. One portion, usually one portion, of the liquid slurry is recycled to the reactor as liquid stream 24 in order to maintain an apparent concentration of . This liquid stream 'B4 is removed from above the upper boiling point sgaO and recirculated to the bottom of the reactor via downflow tube 24 and bong 1B5f and passed above distributor alYt. The pump can be located outside the reactor. Spent catalyst is removed from connection 26 to maintain the desired catalytic activity within the reaction zone.

Reactor operating conditions were 371.1-498.9°C (7oo~
9210'P) and 70.81-851°54
Hydrogen partial pressure of 1000-5000 psi, preferably 898.9-482.2°C (750-9
00″F) and 70.81~281,2δr4/cW
The throughput or space velocity of the coal is maintained in the range of hydrogen partial pressure from 1000 to 4000 psi.
8.815 t (1ft') 118.898~1
18L981 f 7 min (IIs ~ 150 tb/h), for which the yield of unconverted coal as charcoal is approximately 6 to 15 wt. of the feed coal without water and ash.
is within the range of The relative sizes of the coal and catalyst particles and boiling conditions ensure that the catalyst is retained in the reactor while ash and unconverted charcoal particles are removed by the liquid reaction product.

The contacting material is removed from the effluent containing almost no solid particles of catalyst at a light gas stream from reactor 20 through line 2 through separator 8 to line 81 and passed to a hydrogen purification step 82. . A stream of medium-pure hydrogen is withdrawn from purification stage 83 via line 881, heated in heat exchanger 28 and passed through line 8δa to reactor go in line l? A liquid stream from separator 80 is removed from line δ4 and recycled as a heated hydrogen stream of 85 to meet the hydrogen requirements in the reactor.
The pressure is reduced at , and the mixture is sent to a phase separator 88 . This separator Fi 28
Operating at 0.0-848.8°C (500-65 G"F) O temperature and near atmospheric pressure, a light liquid stream is removed from line δ9 and heavy hydrocarbon liquid +5!t line 44. Line The light liquids stream flowing 89 bays contains naphtha and a light effluent pipe section and is sent to a fractionation step 40 from which a hydrocarbon gas product is removed through line 4I and light effluent product pipe line 42. Generally, Contains asphaltenes, glare asphaltenes, unconverted coal and ash solids.
A hydrogenated coal liquid portion having a normal boiling point range of 0 to 1050'F) exits line 44 and is mixed with acid from line 45 and sent to acid precipitation step 46. The ratio of acid flow from line 45 to asphaltenes in the stream of line 42 is approximately δ to 5
The O-line 42 stream, which should be in the range of Iif-1, is typically about 204-1315.6°C (approximately 400-
60 G"F) and pressure sufficient to avoid evaporation of the precipitated acid, typically about 8.52 Kg/ctn.
” (about 50 prig), normal 14.06?/c
Maintain pressure conditions at a pressure not exceeding approximately JILO. Overflow liquid with reduced solids concentration
line 47 and recycled to the reactor 20, typically as a coal slurry oil, via line 1s to maintain a controlled solids concentration in the reactor and further increase the conversion yield of low boiling hydrocarbon products. A downstream liquid stream containing a high concentration of acid and coal solids is transferred to line 48.
In order to facilitate the removal of the downstream liquid stream from the extraction line 48 from the acid precipitation step 46, sufficient mixing and continuous stirring is carried out using equal mixing means across the rotary device 49 to achieve early solidification of the precipitated solid components. It can be prevented. Because the acid and coal-derivative liquid combination is effective in total precipitation of the solids, the residence time in the settling tank in which the solids are settled is usually about 45 minutes or less, preferably 1.
It is 5 to 80 minutes.

Overflow liquid from the settling tank 46 is continuously removed from the line. This overflow liquid contains solids consisting of fine particles of unturned coal and ash in a proportion of less than about 2.0% by weight. This overflow liquid also contains a small amount of acid and is preferably recycled to reactor 20 via line 15t as coal slurry oil for further reaction. A downstream liquid stream of increased solids concentration is sent from settling tank 46 via line 48 by bong 1 action and with the aid of internal rotary rake 49, reduced in pressure in flash drum 50 and sent to vacuum distillation stage 58. This Book Shudrum 5
0t;i at least about 0.85 h/c for evaporation of acid;
m (approximately 59BLg) and 287.8”0 (5
Product overhead liquid is removed from the zero vacuum still 52 via line 58, which is maintained at a temperature of 50" F.
The nonaqueous cannulate product stream is removed from line 54 by mixing with the stream sent via line 48 from the liquid fit fractionation step 40 . True 9 distiller 5 containing a quantity of as7 artene and unconverted coal! The heavy canned liquor stream from J is removed through line 56. The heavy bottom liquor and ash solids from line 5B can be further processed by coking to recover the oil product or gasified to produce the make-up hydrogen required for the process. Although preferred examples have been described, the present invention can be modified in various ways without departing from the scope of the present specification and claims.

[Brief explanation of drawings]

The attached drawings show the method of the present invention using the acid precipitation step for removing all glare 7 artene and coal solids 12...Separation device 14...Slurry tank 16...Bon 1 18...Heater 20...・Reactor
21...Flow distributor 22...Catalyst bed
21a - Boiling upper limit 80.88... Phase separator
δ2...Frozen confectionery purification process 40...Fractional distillation process 46...Acid precipitation process (sedimentation tank) 49...Internal rotary rake 50...Flash drum

Claims (1)

[Claims] L (a) Coal is made into a slurry before processing and induction,
This coal-hydrogen slurry is maintained at high temperature and pressure to hydrogenate the coal with hydrogen and fed into a catalytic hydrogenation reaction zone; the reacted hydrocarbon effluent material is removed; Phase separation yields gaseous and liquid portions; (Cl acid is added to the resulting separation residue liquid portion to precipitate asphaltenes and coal solids; (column containing reduced concentration of luasphaltenes and solids) top liquid f
(61) for further treatment of the heavy hydrocarbon stream containing precipitated glacephaltenes and coal solids; Take out;
and (fl) Coal hydrogenation process for producing hydrocarbon liquid and gaseous products characterized by withdrawing a hydrocarbon liquid product stream containing low sulfur and low ash. 9℃ (70
Temperatures ranging from 0 to 980″F) and 70.81 to 85
1.54111i/cm (1000~5000 psi
The method for hydrogenating coal according to claim 1M1, wherein the hydrogen partial pressure is in the range of g). & Adjust the temperature of the acid precipitation step to about 204.4-815.6℃ (
400 to 60Off). 4 The pressure of the acid precipitation step is approximately 8.・52～85.15K
9/CIL" (approximately 50 to 500 psig). a- The acid added to the coal-derived liquid portion is a Coal hydrogenation method according to claim 1 O a which is approximately 8-6% by weight added to the liquid portion 111 HOt, H, So,
, ■, PO1, BF, or htct8. The method for hydrogenating coal according to claim 1. y. The coal hydrogenation method according to claim 1, characterized in that: y, an acid is added to the liquid portion. & Acid tl-AtCt8 added to the liquid portion.Claim 1: The coal hydrogenation process OL according to claim 1.A patent claim wherein the precipitated residue material from the acid precipitation step is vacuum distilled to recover a clean hydrocarbon liquid product. Coal hydrogenation method according to claim 1 01 α Coal hydrogenation method according to claim 1 in which the overhead material from the phase separation step is fractionated to obtain a gas product and a distillate liquid product A method for hydrogenating coal according to claim 1, wherein the acid added to the O11 solid precipitation step is recovered for reuse. 1. (a) Making coal into a slurry before process-induction;
Is this coal-tomari slurry mixed with hydrogen? 871.1-498.9°C (700-980 ff
') temperature and 70.81 to 851.54 degrees 3 (
1000-50001) 81g') Catalytic militarization reaction while maintaining hydrogen partial pressure 1]! IK supply; y) Reacted hydrocarbon effluent material? and phase-separate this effluent material to obtain a gaseous and liquid portion; i) produce an acid; the separated residue liquid portion has a concentration of about 104.4 to 815
．． 6° C. (approximately 400 to 600” P) (2) m degrees in the range to precipitate asphaltenes and coal solids; A heavy hydrocarbon stream containing precipitated luasphaltenes and coal solids is removed for further processing. ; and +fl a process for producing hydrocarbon liquid and gaseous products, characterized in that a hydrocarbon liquid product i containing low sulfur and low ash is withdrawn.