KR820001971B1 - Combined coal liquefaction-gasfication process - Google Patents

Abstract

The title process was disclosed in which all of the raw feed coal for the process was supplied directly to the liquefaction zone, with the product slurry contg. hydrocarbon gases, dissolved liquid coal, solid dissolved coal and suspended mineral residue from the liquefaction zone being recycled and the remainder being passed to the gasification. The ratio of recycle portion to feed coal being established so that the net yield after recycle based on dry feed coal of solid dissolved coal was <= 17.5 wt % and the net yield after recycle based on dry feed coal of 230-450≰C dissolved liquid coal was >= 35 % than the net yield of solid dissolved coal.

Description

Continuous liquefaction-gasification method of integrated coal

1 shows that the coal liquefaction process is not combined with the gasification process.

2 shows the coal liquefaction and gasification processes combined.

3 shows the yield of distilled liquid.

4 shows the effect of changing the feed coal concentration at a constant recycle slurry concentration.

5 shows the effect of varying the recycle slurry concentration at a constant feed coal concentration.

6 shows the effect of varying feed coal concentration at a constant sum of feed coal and recycle slurry.

7 shows a process in which a gas becomes a liquid.

The present invention relates to an integrated coal liquefaction and vaporization process comprising a coal solvent liquefaction zone and an oxidative vaporization zone.

In the vaporization zone all feeds contain undissolved coal and mineral residues suspended from the liquefaction zone, with hydrogen derived from the vaporization zone being consumed in the liquefaction zone.

All feedstock coal in the joining process is fed directly into the liquefaction zone and is not particularly feedstock coal or other hydrocarbon feedstock directly into the vaporization zone.

The feed coal may be bituminous coal, sub-bituminous coal or lignite, and the liquefaction zone of the process includes an endothermic preheating step in which the hydrocarbon material is decomposed into mineral residues, hydrocarbon gas, naphtha, dissolved liquid coal, It usually includes an exothermic melting step that produces a mixture consisting of coal dissolved in solids and mineral residues. The temperature in the dissolver is higher than the maximum preheat temperature because of the hydrothermal reaction, which is exothermic and the hydrocracking reaction takes place in the dissolution step.

Residues and slurries from other steps in the dissolution step or in the process involving the solvent liquid and the mineral residue are recycled through the preheating step and the dissolving step. Gas hydrocarbons and liquid hydrocarbon distillates are recovered from the liquefaction zone separation stage.

The mineral-comprising residual slurry portion from the dissolution step is recycled and the residue is passed through atmospheric pressure and vacuum distillation column.

All normal liquid and gaseous products are removed from the tower and mineral remains, i.e. solid dissolved coal and mineral residues from the liquefaction zone, remain at the bottom of the vacuum tower. Normally liquid dissolved coal products having boiling points of 232 to 454 ° C are called "distillate liquid" and "liquid coal" and the dissolved coal is liquid at room temperature and contains a treating solvent.

The slurry contains organic matter (U0M) which is vaporized and insoluble in the raw mineral and raw coal, together referred to herein as the "mineral residue".

The amount of UOM is always less than 10 or 15 percent by weight of the supply coal.

The VTB slurry vaporizes the dissolved coal from the liquid zone at 454 ° C. + and the 454 ° C. + dissolved coal is solid at room temperature and is referred to herein as normally solid dissolved coal. The non-recycled VTB slurry is passed all the way through the partial oxidizing gas zone to receive a slurry feed for conversion to syngas, a mixture of carbon monoxide and hydrogen, without filtration or other solid / liquid separation steps, without coking or other steps of destroying the slurry. .

The slurry is a carbonaceous feed and feeds into the gasification zone.

The oxygen system is installed to remove nitrogen in particular from the syngas generated from the air supplied to the vaporizer. At least part of the syngas is subjected to a time-shift reaction to replace hydrogen and carbon dioxide.

Carbon dioxide, together with hydrogen sulfide, is recovered in the degassing apparatus and all gaseous hydrogen streams produced in particular are consumed as treated hydrogen in the liquefaction zone. Treated hydrogen can be obtained from syngas by passing the syngas at low temperature or by absorption separating the hydrogen stream from the carbon monoxide stream.

The hydrogen stream can be used as process hydrogen and the carbon monoxide stream can be used as process fuel. The residence time and other conditions control the dissolution stage and hydrocracking reaction of the liquefaction zone. Consistent with the present invention, these conditions are established to yield yields based on dry feed coal of 232 to 454 ° C. mid-liquid liquid and the most preferred product is yield based on dry feed coal of 454 ° C. + usually solid dissolved coal. Greater than at least 35,40 or 50% by weight.

Figures 1 and 2 discussed below show that the process of the present invention and the part of the liquefied liquid are combined with the process conditions that usually transform into solid dissolved coal, and the yield of distilled liquid is unexpectedly high due to the reduced residence time. Can be increased.

The relatively low dissolved material residence time (i.e. small dissolved material size) and relatively low hydrogen consumption in the bonding process of the present invention is shown below and the liquid distilled from the resulting product is 35,40 or 50% by weight of dissolved coal or more. Large dissolved substances and hydrogen consumption (reduces product in the fraction of the distilled liquid to obtain a normally solid dissolved coal).

It is usually believed that elevated fractions of liquid coal in solid dissolved coal require relatively large dissolved substances and relatively high hydrogen consumption. It is a further development of the present invention that a portion of the liquid coal is elevated to solid dissolved coal, with a smaller fraction of the liquid coal being achieved with less gasification than is usually required for solid dissolved coal.

The liquid fraction distilled between 232 and 454 ° C. is the most valuable liquefaction zone product fraction and is more valuable than the low boiling product fraction because of more fuel than is recovered. The naphtha product fractionation on the cross section needs to be graded by reforming and catalytic hydrotreatment to convert the fuel to calcined coal. Distillation fractionation is more valuable than fractionation of solid dissolved coal, usually at high boiling points, because high boiling fractions are not liquid at room temperature and contain mineral residues.

The gradual increase in the fraction of the distilled liquid into relatively normal solid distilled coal is achieved by gradually lower process consumption levels and vice versa. The reason for reducing hydrogen consumption in the mixing process of the present invention, which is a selective development for making distilled liquids, usually solid dissolved coal, is a distilled liquid and does not extend the low boiling products, naphtha and hydrocarbon gas.

Increased distillate yields obtained in accordance with the present invention can be obtained not only by decreasing yields of ordinary solid dissolved coal, but also by reducing the yields of unexpected naphtha and gaseous hydrocarbons.

The yield of distilled liquid can be increased gradually with decreasing residence time, while the yield of other main product fractions is high and the low boiling hydrocarbon fraction is reduced. The prior art of coal liquefaction and gaseous liquor is described in "SRC-II process in B.K. Schmid and D.M. Jackson's Coal Vaporization and Liquefaction, International Reference 3rd Annual 8will 3-5, 1976."

The technique shows that in coal liquefaction-gasification combinations, organic material passes from the liquefaction zone to the vaporization zone to produce the hydrogen needed for the process.

Table I of the present technique only shows dissolution elution data and these data by extraction are obtained as a liquid distilled at 232 to 454 ° C. and yields about 27% greater than the usual solid dissolved coal at 454 ° C.

Figures 1 and 2 show a yield of at least 35 or 45 percent at residence time (i.e. dissolved material size) of the present invention, preferably between 232 and 454 캜. The yield of distillate 454 ° C. + normal solid dissolved coal is at least 50 percent, and the extraction data in Table I of the present technique shows that the yield of 232 to 454 ° C. distillate is 25.69 wt%, the most preferred product fraction.

Figures 1 and 2, discussed below, show that the liquefaction-vaporizer integrated with the maximum dissolution of the desired product fraction (27% by weight) that can be obtained in a non-integrated process is controlled by the inventive dissolution residence time. It is shown that a high yield of liquid can be obtained.

VTB, like the liquefaction zone, includes the overall yield of normal solid dissolved coal in the 454 ° C + liquefaction zone. This is because unrecycled VTB passes through the vaporization zone and does not go through the separation of mineral residues from the dissolved coal. That is, solvent extraction of hydrogen-excess compounds from hydrogen-small compounds, including filtration, fixation, specific solvent-assisted fixing, mineral residues or centrifugation, is used. The vaporization temperature is 1,204 to 1,982 ° C and all minerals from the liquefaction zone melt to form molten slag which is cooled and removed from the vaporization as a stream of solidified slag.

The use of vacuum distillation units in this process ensures the separation of hydrocarbon gas from liquid coal and 454 usually solid dissolved coal to the vaporization zone. Passing the liquid coal into the partial oxidization vaporization zone requires a relatively high hydrogen consumption to produce excess fuel. Conversely, solid dissolved coal is usually suitable for gasification with low hydrogen content.

The mineral residues obtained from the liquefaction zone consist of catalytic materials for solvation, selective hydrogenation and hydrocracking of dissolved coal to the desired product. The recycling of mineral residues increases so that the concentration in the liquefaction zone increases with the ratio of the selective hydrocracking of the dissolved coal, and the slurry residence time required for the dissolved material and the required size of the dissolved material decrease.

Reduced residence time in the presence of increased mineral residues increases coal conversion and reduces the amount of undesirable product form, usually solid dissolved coal and hydrocarbon gas.

Mineral residues are suspended in small particle size dissolved solids eluting slurries with 1 to 20 micron small particle morphology and enhanced catalysis with increased surface area and recycled from the slurry with liquid and usually solid dissolved coal distilled from the mineral material. Let's do it.

The recycled distillation liquid provides a solvent for the normally solid dissolved coal recycled with the process according to the product fraction in order to reduce the residence time so that it can react. Catalysts and other effects due to the recycling of mineral residual slurries can be reduced by half or more, usually through the selective hydrocracking of dissolved coal, or likewise with the increased removal of sulfur and oxygen, the yield of normally solid dissolved coal in the liquefaction zone. have. Therefore, recycling mineral residues has an effect on the efficiency of the integrated liquefaction-gasification process.

Hydrocracking cannot be satisfactorily achieved by increasing dissolved material temperature without inhibition via exothermic reactions that occur because excess coke is formed and selective hydrogen consumption is inhibited.

The use of an external catalyst in the liquefaction process increases the cost of the feed coal and complicates the process, so the introduction of the external catalyst does not recycle mineral residues, and the process efficiency decreases with the use of the catalyst.

For this reason, this process does not require the use of an external catalyst.

In the process of the present invention, the method of using the recycled air stream in the vaporization zone and the liquefaction zone is highly dependent on each other. The net yield of solid dissolved coal at 454 ° C. is obtained from the liquefaction zone, which consists of the entire hydrocarbon feed for the vaporization zone.

The gasification zone may produce fuel for the bonding process with hydrogen.

454 ° C + The amount of solid dissolved coal and the UOM vaporization zone are required for the liquefaction zone, depending on the process hydrogen and fuel purpose. Treated hydrogen and fuel requirements affect the recycling of feed coal to the liquefaction zone of the corresponding mineral residues. This is because the recirculation ratio of mineral residues and 454 ° C + normal solid dissolved coal affect the 454 ° C + normal solid dissolved net yield obtained from the liquefaction zone to pass through the gasification zone. The recycled mineral residue consists of a catalyst for the conversion of dissolved coal and a recycled material of solid dissolved coal, usually the net yield of solid dissolved coal and the UOM are all hydrocarbonaceous since the vaporization zone depends on the recycle ratio of mineral residues. It consists of a feed.

Yields of solid dissolved coal and recycled mineral residues from suspended solids and ordinary solid dissolved coals are quantified for non-normal product selectivity retention times, as described in Figure 2 and shown in Figure 2. Strictly contrasts with relationships and appears to be non-reacting processes.

For this reason, the elevated portion of the liquid 454 ° C. + normal solid dissolved coal distilled from 232 to 454 ° C. according to the present invention is recycled to the gasification zone by recycling the 454 ° C. + normal solid dissolved coal and liquefaction zone or passing through the vaporization zone. Critical to all processes of suspended mineral residues obtained by feeding the hydrocarbon feed.

The process of the present invention is capable of exchanging various process conditions. Because the mineral residue-containing recycle air stream is mixed with the raw coal containing the feed slurry in the liquefaction zone and needs to be solid at both the feed slurry or near maximum level.

All solids are not forced due to pump capacity problems.

While maintaining the feed coal ratio, it is important that the process be kept at or near the total solids in order to obtain the maximum amount of recycled mineral residues. Forcing the total solids at the recycle ratio of mineral residues needs to be reduced as opposed to the feed coal ratio.

Consistent with the present invention, liquefaction and gasification operations are combined in a highly sufficient operating method.

At high heat, the liquefaction process is usually more effective than the vaporization process at the normal yield of solid dissolved coal, and in U.S. Application No. 905,229, the integrated coal liquefaction vaporization process meets the total hydrogen demand in the liquefaction zone when syngas is produced in the vaporization zone. In addition to the supply, combustion directly in the process of syngas or in excess carbon monoxide streams derived from them enhances at least 5 or 10 percent and even 100 percent by the thermal criteria of the overall process energy requirement. The total energy required for the process includes electrical or other energy but does not include the heat generated in the vaporization because the exothermic vaporization heating reaction is believed to heat the water.

It is surprising that the fixed efficiency can be enhanced by a limited increase in the amount of solid-melted coal vaporized than by the conversion of coal in the liquefaction zone, while coal vaporization is not an effective method of coal conversion than coal liquefaction. Known.

It is believed that the addition of process energy to the hydrogen process produces the necessary products, which tension the gas zone and reduce the efficiency of the bonding process. The bath is pre-hydrogenated as with raw coal, so the vaporized coal is not supplied enough, so the reaction in the vaporization is oxidation.

Despite these investigations, the U.S. Patent Application No. 905,299 discloses that the thermal efficiency of the integrated liquefaction-vaporization process produces a significant amount of process carbon with gasification of syngas, or an excess of carbon monoxide gas derived from syngas, as well as treated hydrogen. It is said to increase when doing so.

The patent application achieves high thermal efficiency when the amount required to produce treated hydrogen is in excess of at least 60% based on the combustion heating of the syngas, and excess carbon monoxide stream derived from the syngas or syngas is hydrogenated or otherwise converted. Used as fuel in the joining process without steps. Most of the syngas produced in the reported devices is processed as reactants and fuels without conversion to other fuels such as methane or methanol.

Syngas may be used for acid gas extraction or for the separation of CO from H ₂ prior to use. Because gasification generally fails to oxidize all of the hydrocarbonaceous fuel supplied and is lost as coke in the removed slack and gasifiers allow the hydrocarbon feed to operate at high efficiency in solid and carbonaceous feeds such as coke and in the liquid state. Because.

Coke is a classified hydrocarbon solid and can be vaporized at nearly 100 percent efficiency, such as a liquid hydrocarbon feed, lost in the molten slack formed in vaporization than in the case of a liquid gasification feed, and there is an unnecessary loss of hydrocarbon material from the device.

As such, the use of coke between the dissolution and vaporization zones reduces the efficiency of the integrated process.

The overall yield of coke in this process (including UOM) is below 1% by weight and below 1-10% by weight based on dry feed coal.

Oxidation-enhanced vaporization rates increase the vaporization temperature.

Such high vaporization temperatures are necessary to achieve high process efficiency and the maximum vaporization temperature of the present invention is 1204 to 1982 ° C, generally 1260 to 1760 ° C, preferably 1316 or 1371 to 1760 ° C. Moreover, the VTB slurry passing through the vaporizer is particularly water free and controls the amount of water or steam and is vaporized to produce CO and H ₂ by endothermic reactions between the water and the hydrocarbon feed.

This reaction consumes heat, producing CO, which generates heat through the reaction of hydrocarbons with oxygen. In the gasification process, H ₂ is the desired vaporization product in the transfer reaction, methanation reaction or methane substitution reaction depending on the vaporization step, and it is advantageous to use a lot of water. Moreover, in the process of the present invention the syngas can be used directly as process fuel as mentioned above, and the hydrogen product is reduced compared to the product of CO which consumes heat, such as CO, H ₂ .

Moreover, the elevated vaporization temperature of the present invention results in complete oxidation of the hydrocarbon feed and the product is in equilibrium with the syngas product at a gasification temperature with a high molar ratio of H ₂ and CO of 0.8 or 0.9 or lower. Moreover, as mentioned above, this equilibrium is not lost in processes where carbon monoxide is used as process fuel.

In the integrated process all feed coal is mixed with a hot solvent containing crushed, dried and recycled slurry. Recycle slurries are generally thinner than slurries passing through the gasification zone because they are not vacuum distilled and contain 232 to 454 ° C distilled liquids and have a solvent function. The recycle slurry, hydrogen and raw coal are passed through a flame preheating zone and then through a reactor or melting zone.

The ratio of hydrogen and raw coal is between 20,000 and 80,000 SCF (0.62 to 2.48 M ³ / kg) and preferably between 30,000 and 60,000 SCF (0.93 to 1.86 M ³ / kg) per ton.

In the preheating step, the temperature of the reactants is gradually increased so that the preheating external temperature is 360 to 438 ° C., preferably 371 to 404 ° C. Coal is partially dissolved at this temperature and exothermic hydrogenation and hydrocracking reactions begin. Heat is generated as an exothermic reaction in the melt and is a relatively uniform temperature and the temperature of the reactants rises between 427 and 482 ° C, preferably between 449 and 466 ° C.

The delay time in the melting zone is longer than in the preheating zone.

The melting temperature is small, 11.1, 27.1, 55.5 or 111.1 ° C, higher than the external temperature of the preheater.

The hydrogen pressure in the preheating and dissolution step is 1,000 to 4,000 psi (70 to 280 kg / cm ² ) and preferably 1,500 to 2,500 psi (105 to 175 kg / cm ² ). Hydrogen is added to the slurry once or several times to add a portion of the hydrogen to the slurry before entering the outlet of the preheater.

Additional hydrogen is added between hydrogen cooling in the preheater and the dissolver and / or the dissolver itself.

Cooling hydrogen is injected in various ways as needed in the dissolver to maintain the reaction temperature and removes the coking reaction.

1 and 2 are graphs illustrating the present invention.

FIG. 2 shows a coal liquefaction process not merged with a vaporizer and FIG. 2 shows the coal coal liquefaction-gasification process of the present invention.

These plots relate to the slurry residence time of the dissolution for the weight percent yield of the 232-454 ° C. distilled liquid and the 454 ° C. + weight% yield of the normal solid dissolved coal, based on dry feed coal. Or C ₁ to C ₄ gas streams; C ₅ 232 ° C. naphtha; The weight percent yield at various sieving times of the weight percent yield of insoluble organics and the weight percent yield of hydrogen consumed based on the feed coal.

The yields shown in FIGS. 1 and 2 are pure yields based on the weight of the liquid zone, based on the moisture-glass feed coal, and are obtained after the removal of all recycle material from the liquefied zone eluent stream.

The process dissolvers of FIGS. 1 and ² are operated at a temperature of 460 ° C. and a hydrogen pressure of 1700 psi (119 kg / cm ² ), and the dissolution time is a process condition that is changed without inhibition. The process described in Figures 1 and 2 is observed at 50% by weight of the total solids for the feed slurry and includes feedstock coal and recycled mineral residue slurries.

This total solids content limits the pumping capacity of the feed sludge. In the Table 1 process, the solid concentration of solid slurry is 30% by weight of feed coal and 20% by weight of recycled solid, and the ratio of feed coal to recycled solid can be kept constant because liquefaction is not combined with vaporization in the process. have.

That is, VTB is not supplied to the vaporizer.

In the process of FIG. 2, the total solids content of the solid slurry is 50% by weight, while the fraction of coal and recycled solids in the feed slurry is changed because the liquefaction zone is combined with a vaporizer that contains a mobile semi-container for process hydrogen setting, In this way, the dissolved eluted solid is passed through the vaporizer, supplying the total hydrogen needed in the liquefaction zone in an amount allowed by the vaporizer (as VTB),

As with the amount of solid-comprising slurry available for recycle in FIG. 2, the ratio of feed coal to recycle solids is determined by the amount of solid-comprising slurry required in the vaporizer.

Figure 1 shows when the liquefaction and vaporization zones do not combine, but the liquefaction zone is provided as a product recycle stream, and remains stable at about 27% by weight, based on the feed coal, at 232-454 ° C distilled liquid yield. While the delay time is increased, 454 ° C + solid coal decreases as the delay time is increased.

Figure 1 shows the yield of distilled liquid, which is the most preferred product fraction and does not increase by more than 27% by weight, regardless of the lag time.

Figure 1 also shows the yield of liquid coal at 232-454 [deg.] C., which is the most preferred product classification and is at least 50% greater than the yield of solid coal at 1.15 hours and beyond.

The vertical dashed line in FIG. 1 has a delay time of 1.15, the yield of solid coal is 18% by weight, and the yield of distilled oil is 27% by weight.

That is about 50 percent higher. Usually, the 50% yield of solid dissolved coal coal decreases with a lag time of less than 1.15 hours but increases with a lag time of more than 1.15 hours and less than 1.5 hours.

Figure 2 illustrates the process, in which the liquefaction zone is integrated with the vaporizer and the liquefaction zone is provided as a product recycle stream, and the vertical dashed line usually yields 50% yield of solid dissolved coal coal at 1.4 hours of dissolution time. Is achieved.

At 1.4 hours of dissolution hold time, the yield of solid dissolved coal is 17.5% by weight, whereas the liquid coal yield is 26.25% by weight. That's about 50% bigger.

Improved yields in distilled liquids are obtained at low delay times of 1.15 hours in unintegrated units. Relatively developing in the dissolution unit period is not caused by a small vaporizer and in the examples is usually solid coal

Combined liquefaction-vaporizers are considered, unless they are phase-produced yields. Ie at least 35.40 or 50% by weight or more.

What is relatively undeveloped in the integrated unit is that the lag time in the integrated unit gradually increases with the increased melter lag time as it usually increases the yield of solid dissolved coal coal. In contrast, in the unbonded unit, the yields of coal-melted liquids, usually solid, gradually increase with an increase in lag time of more than 1.15 hours and less than 1.5 hours.

The solid coal yield and the solid dissolved coal yield at the vertical dashed line in FIG. 2 are almost identical for the yield of the corresponding product at the vertical dotted line in FIG. 1, respectively.

Moreover, a particularly notable process condition in the vertical dashed line in FIG. 2 is reduced in dissolution delay time and the yield of 232-454 ° C. liquid coal product fractionation in the yield of 232-454 ° C. liquid coal can be obtained in the process of FIG. 1. There is no increase in dissolution time.

Notably, the process conditions decrease without an increase in lag time, represented by the vertical tangent of FIG. 2 and increase to above-maximum levels of liquid coal fractionation at 232-454 ° C. and can be achieved without dissolution device lag time in the process of FIG. have.

(Ie at least 27% by weight, preferably at least 28,29 or 30% by weight)

The skew yield of the 232-454 ° C. liquid coal yield shown in Table 1 of the above-cited literature is 25.65 weight percent and is no greater than 27 weight percent of this classification obtained in the unbound liquefaction process of FIG.

In the combined liquefaction-vaporizer in FIG. 2, the enhanced yield of solid-dissolved coal distilled liquids is increased by more than 50% in melter lag times of less than 1.4 hours, which is surprising and also diagonally in FIG. It is the opposite position and is 50% yield in order to gradually reduce the distilled liquid at a lag time of less than 1.15 hours.

In FIG. 2 of the present invention, the reduced dissolved material and the reduced hydrogen consumption are gradually increased at less than 1, less than 0.4 or 0.5 hours or less of the dissolver lag time.

The progressively increased ratio of liquid coal, usually an important one shown in FIG. 2, to solid dissolved coal is achieved with progressively less hydrogen consumption and appears to be less of the required vaporization size.

As pointed out above, this is groundbreaking because the selective development in the bonding process can be made directly with the yield of distilled liquid.

FIG. 2 shows that the increase in liquid coal obtained is not only reduced in the yield of solid coal, but also unexpectedly achieved by lower yields of naphtha and gaseous hydrocarbons. Thus, unexpectedly, the yield of liquid coal increases gradually, while all other The yield of the product increases and the low boiling product decreases.

Filling the combination of liquefaction and vaporization operations in the process of the references cited above provides a hydrogen balanced device.

Reference is made to the dissolution apparatus elution data shown in Table I.

These extrapolated data show that the oil yield distilled 232-454 ° C. in the reference step is 27% by weight greater than the yield of 454 ° C. + solid coal.

가량 큰 용해물질 크기이다.FIG. 2 shows the improved 27-wt% yield of 454 ° C. + normal solid dissolved coal phase 232-454 ° C. liquid coal in the combined device of the present invention requires a dissolution time of 1.9 hours and a yield of 50% cent or more. Than the dissolved substance size

This is a large dissolved substance size.

The reduction in dissolution time in FIG. 2 is achieved when the yield of liquid coal 232 to 454 ° C. on 454 ° C. + usually solid dissolved coal is increased by at least 27% by weight to at least 60, 70 or 80 or 100% or more. .

In the integrated coal liquefaction-vaporizer of the present invention, one finds a surprising effect of the lag time on the relative yield of liquid coal and usually solid dissolved coal.

The present invention is described in part in FIG. 2 and shows dry coal concentrations and recycle solids (recycle tribute residues) concentrations, each for a total of 50% by weight of feed slurry in a feed slurry of three different dissolution lag times in the binder. Has a solid inhibition.

As shown in FIG. 2, reduced dissolution time is achieved with increased recycled solids concentration and reduced dry coal concentration, and in feed slurry, has a beneficial effect of high recycled solids level.

The present invention is better described in FIG. 3 and shows data for using product liquefaction with combined liquefaction-gasifiers in hydrogen balance and feed slurry mixing tanks with total solid suppression.

Figure 3 shows the increase in liquid coal yield due to the increased concentration of recycled mineral residues derived from the feed slurry, which is reduced in the induction of melter lag time, resulting in a decrease in the constant total solids coal concentration.

The internal constants of FIG. 3 show that the yield of distilled liquid at 232 to 454 ° C. is obtained at various delay times at both inhibition levels of feed coal plus recycle solids (50 and 45 wt%) in the feed slurry.

In FIG. 3, the increased distilled liquid yield of each of the two inhibitory total solids is shown as a decrease in the dissolution time.

3 shows that the increase in the yield of distilled liquid in the suppressor is achieved by the reduced concentration of raw coal in the feed slurry and the overall solids level in the feed slurry is constant along the two lines of FIG. The increase in the yield of liquid coal is shown to lead to an increase in the ratio of recycled mineral residues to raw coal in the feed slurry.

2 and 3 extend in FIGS. 4, 5 and 6 and FIG. 4 shows an increase in the concentration of raw coal in the feed slurry to the yield of liquid coal at a constant concentration of the recycle slurry.

5 shows an increase in the concentration of recycled mineral residues in the feed slurry with respect to the yield of distilled liquid at a constant concentration of feed coal. Finally, FIG. 6 shows the feed slurry of feed coal at the concentration of feed coal plus recycled solid residue. Change in the concentration of raw coal in the feed slurry, the comparison of Figures 54 and 5 increased the feed coal concentration and recycle slurry concentration, but the yield of distilled liquid increased in the feed slurry, respectively. The effect of change in the recycle slurry concentration on is about 3 times the change in feed coal concentration.

FIG. 6 sums the data of FIG. 4 and FIG. 5 and shows this increase in feed coal concentration, which occurs in the expansion of recycle solids.

In other words, when the total solid is suppressed, the liquid yield actually distilled has a negative effect.

The experimental diagram of the mixing process of the present invention is illustrated in FIG.

Dry, pulverized raw coal The entire raw coal feed is passed through line 10 to slurry mixing tank 12 and mixed with hot solvent-containing recycle slurry from line 14.

In line 16, the solvent-containing recycle slurry mixture (slurry weight 1.5-2.5 parts range for 1 part coal) is maintained at an inhibitory total solid level of about 50-55% by weight and pumped with a reciprocating pump 18 and Mixing with recycle hydrogen through 20 and injecting hydrogen through line 92 before passing preheating tube 22 from line 24 and dissolution unit 26.

The ratio of hydrogen and feed coal is about 40,000SCF / ton (1.24M ³ / kg). The temperature of the reactants at the outlet of the preheater is 371 to 404 ° C. at which temperature coal is partially dissolved in the recycle solvent and exothermic hydrogenation and hydrocracking reactions begin.

The temperature is gradually increased with the length of the preheater tube and the dissolving unit is generally homogeneous and heat is generated by the hydrocracking reaction in the dissolving unit and raises the temperature of the reactant in the range of 449-466 ° C.

The reaction temperature of the cooling hydrogen passing through the line 28 is adjusted, and the impact of the exothermic reaction is reduced and injected into the dissolution apparatus.

The melter eluate is passed through line 29 to a vapor-liquid separator 30. The hot steam stream from these isolates is cooled in a heat exchanger and an additional vapor-liquid separation step and removed via line 32.

Liquid distillates from these isolates are passed through line 34 to atmospheric separator 36.

A non-concentrated gas is passed through an acid gas removal unit 38 to remove H ₂ S and CO ₂ in a line 32 consisting of unreacted hydrogen, methane and other light hydrocarbons, plus and CO ₂ .

The recovered hydrogen sulfide is converted into sulfur element and removed by passing through line 40. The refined gas is passed through line 42 and carried out in a cryostat 44 to remove excess of the pipeline gases methane and ethane and through line 46 to remove LPG propane and butane and Pass it to (48).

The pipeline gas in line 46 and LPG in line 48 represent the pure proportion of these materials from the process.

Purified hydrogen (90 percent pure) in line 50 is mixed with recycled hydrogen for processing with the gas remaining from the acid gas treatment of line 52.

Liquid slurry is passed from the vapor-liquid separator 30 to the line 56 and separated into two main streams 58 and 60. Air stream 58 consists of a recycle slurry comprising a solvent, usually solid dissolved coal and catalytic light residues, wherein the non-circulated portion of the slurry is atmospheric pressure through line 60 to separate the main product of the process. Pass the classifier 36.

The fractionator 36 distills the slurry product at atmospheric pressure to remove the upper naphtha stream, passes through line 62, passes through the half distilled stream through line 64, and passes the bottom stream through line 66. In air stream 62, naphtha shows the net yield of naphtha from the process. The bottom stream in line 66 passes through the vacuum distillation tower 68.

The temperature of the feed into the fractionator is normally maintained at a sufficiently high level without the need for additional preheating than starting the operation.

In line 64 a mixture of fuel oil from the atmospheric pressure and the half distilled material recovered from the vacuum tower via line 70 is recovered via line 72, making the main fuel oil product of the process. In line 72 the air stream consists of fuel liquid products distilled at 232-454 ° C. and these portions are fed to feed slurry mixing tank 12 via line 73 to control the solid concentration in feed slurry and coal-solvent ratios. Can be recycled.

The recycle stream (73) can be recycled to impart flexibility to the process at the ratio of solvent to slurry and not to adapt the ratio to the process at the ratio using line 58, and also improve the pumping capacity of the slurry.

The portion of air stream 72 not recycled through line 73 is the net yield of liquid distilled from the process.

The vacuum column consists of all non-recycled solid dissolved coal, undissolved organics and minerals without any distillate or hydrocarbon gas stream and passes through partial oxidization zone 76 through line 74. .

The vaporizer 76 is matched with the receiver and the hydrocarbonaceous slurry feed stream so that a hydrocarbon conversion step such as coke does not occur between the vacuum tower 68 and the vaporizer 76 and destroys the necessary reslurrying in the slurry and water. do. The amount of water needed for the slurry coke is greater than the amount of water initially required by vaporization because the amount of water evaporated is reduced in the amount of heat consumed in the vaporization stage.

Nitrogen-free oxygen for vaporizer 76 is produced in oxygenator 78 and vaporized through line 80.

Steam is fed to the vaporizer via line 82, and the total mineral content of the feed coal supplied via line 10 is removed from the process as an inert slack via line 84 and from the bottom of vaporizer 76. Release.

Synthesis gas is produced in the vaporizer 76 and these portions are steam and CO carried out by the acid gas removal zone 89 to remove H ₂ S and CO ₂ to convert to CO ₂ and H ₂ S Pass through line 86 to mobile reactor zone 88 for conversion.

The obtained purified hydrogen (purity 90 to 100%) is compressed through the compressor 90 to the process pressure and supplied through line 92 by producing hydrogen for the preheating zone 22 and the dissolution device 26.

The amount of syngas produced in the vaporizer 76 supplies all the hydrogen molecules required by the process but preferably can provide sufficient energy for the process and between 5 and 100% of the barrel without the methanation step. . By the end, the syngas portion does not flow through the acid gas removal unit 96 through line 94 to the mobile reactor and CO ₂ and H ₂ S are removed from them. Removal of H ₂ S is accomplished by syngas being the required ambient standard of the fuel, while removal of CO ₂ increases the heat consumption of the syngas so that microheat control can be achieved when used as fuel. The stream of purified syngas passes through boiler 98 to boiler 100.

Boiler 100 provides the consumption of syngas as fuel.

The water stream passes through the line 102 to the boiler 100 and is converted to steam and supplies process energy through the line 104 (ie, using something like a reciprocating pump 18). A separator stream of syngas from the acid degassing removal unit 96 is passed through the line 106 to the preheater 22 for use as fuel. Syngas can be used anywhere in the process as the required fuel. If the syngas does not provide enough of all the fuel required for the process, the remaining fuel and the fuel required for the process can be supplied from a non- surcharge fuel stream directly produced in the liquefaction zone. If this is economic, all energy for the process can be supplied from an external source, not shown, such as power, unless it is derived from syngas.

Additionally, syngas passes through line 112 to mobile reactor 114, increasing the ratio of hydrogen to carbon monoxide to 0.6-3. This increased hydrogen mixture is passed through line 116 to methanation unit 118 to convert the pipeline gas and through line 120 to mix with pipeline gas in line 26. If a high thermal efficiency of the process is obtained, the amount of pipeline gas based on the heating value through line 120 is less than 40 percent or the amount of syngas used as process fuel passing through lines 28 and 106.

The purified syngas stream portion is passed through the line 122 to the low temperature separation unit 124 and the hydrogen and carbon monoxide are separated separately.

Absorption units can be used at low temperature units and excess hydrogen stream can be recovered via line 126 and mixed with the hydrogen stream produced in line 92, passing the liquid or solid region as a product of an independent process. . Large amounts of carbon monoxide streams can be recovered through line 128 and mixed with syngas used as process fuel in line 98 or line 106 and sold and can be used independently as process fuel or chemical feedstock. have.

7 shows that the gasification section of the process becomes a liquefaction section.

The entire feed to the gasification section (VTB) is derived from the liquefaction section and most or most of the gaseous product of the gasification section is consumed in the process as a reactant or fuel.

Claims (1)

For the production of liquefied effluent mixtures consisting of hydrocarbon gas, dissolved liquid coal and suspended mineral residues, hydrocarbons from mineral residues are dissolved and minerals containing minerals for pyrolysis, hydrogen, recycled dissolved liquid solvent, at room temperature Transfer solid solvent recycled coal, recycle mineral residue to coal liquefaction area, After recycling, the net yield based on dry feed coal of solid dissolved coal is 17.5% by weight or less, and the net yield based on dry feed coal of dissolved liquid coal of 230 ° C to 450 ° C is at least 35% by weight. By adjusting the recycle ratio of the feed coal to recycle the dissolved liquid coal, solid dissolved coal and mineral residue to the liquefaction zone, The dissolved liquid coal and hydrogen gas are separated from the solid dissolved coal and the mineral residue in order to produce a vaporizer feed slurry having a pure rate of mineral residue and solid dissolved coal in the liquefied region. Introducing the vaporizer feed slurry into a gasification zone comprising an oxidation zone to convert hydrocarbon material into syngas; Converting at least a portion of the syngas into a hydrogen gas rich fluid, To transfer hydrogen-rich fluid to the liquefaction zone for hydrogen supply. A liquefaction-vaporization method of mixed coal which consists of.

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