CN1107540C - Dispersion anion-modified and phosphorus supporting ferric oxide catalyst - Google Patents
Dispersion anion-modified and phosphorus supporting ferric oxide catalyst Download PDFInfo
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- CN1107540C CN1107540C CN98122746A CN98122746A CN1107540C CN 1107540 C CN1107540 C CN 1107540C CN 98122746 A CN98122746 A CN 98122746A CN 98122746 A CN98122746 A CN 98122746A CN 1107540 C CN1107540 C CN 1107540C
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Abstract
The present invention discloses a dispersed slurry catalyst of iron oxide, which has fine granularity, anion modification and phosphorus assisting catalysis. The catalyst has large surface area, small particle size and high catalytic activity, wherein the surface area is larger than about 100m<2>/g, and the particle size is smaller than about 50 angstrom. The catalyst is formed by the synthesis and the quick precipitation of saturated water solution, such as saturated water solution of iron sulfate and saturated water solution of iron alum, and phosphorus is used for assisting catalysis. The catalyst can be used in the mode of a wet cake or gel which is easy to be mixed with carbon-containing raw materials (such as coal, heavy oil, mixed waste plastic or mixtures of the coal, the heavy oil and the mixed waste plastics), or the catalyst is added in the mode of fine particles after the catalyst is dried and/or calcined. The present invention comprises a method for preparing the catalyst and a process for preparing the needed liquid hydrocarbon products with low boiling points by the hydrotreating of carbon-containing raw materials.
Description
The present invention is the application number No.08/609 that submitted on February 23rd, 1996,759 part renewal application.
The present invention relates to the iron oxide slurry attitude catalyst of the sulfate anion modification of high degree of dispersion, this catalyst has the catalytic activity of high surface area and high hydrocarbon hydroconversion reactions.The present invention be more particularly directed to such decentralized ferric oxide catalyst, this catalyst is by from sulfate radical (SO
4 2-) anion exists to be precipitated out rapidly in the molysite saturated aqueous solution down and make, and help catalysis as the co-catalyst of hydrocracking/hydrogenolysis by the adding carbamate additives for low phosphorus.This disperse type catalyzer can be used for the hydroconversion reactions of carbon raw material (as coal, heavy crude residual oil) and other high-molecular-weight hydrocarbons (as waste plastics), to make the required high liquid hydrocarbon product of lower boiling surcharge.
Permitted just to know that various iron containing compoundses are (as pyrite (FeS many years ago
2) and red soil (Fe
2O
3)) can in coal hydrogenation and liquifying method, be used as catalyst.These iron catalyst compound particles are usually with in the coal-slurry oil attitude feed stream that is added in the reactor upstream of operation under the high-temperature and high-pressure conditions on a small quantity.Yet, (this mainly is because their initial surface area is lower because the efficient of these known catalytic compounds is lower usually, high-caliber decentralization (the catalyst granules number of unit reaction volume) can not be provided under reaction condition), the catalytic hydrogenation conversion process of therefore developing coal and heavy crude residual oil raw material in the past in 30 years adopts the granular pattern carried catalyst usually.These carried catalysts can be to contain a small amount of one or more to be deposited on the bead or the extrusion modling thing of the active catalytic metals (as cobalt, molybdenum or nickel) on the inert support material (as aluminium oxide or silica).Some examples of these granular pattern carried catalysts are disclosed in U.S. Patent No. 3,630, among 888 (Alpert etc.), 4,294,685 (Kim etc.) and 4,424,109 (Huibers etc.).That these carried catalysts can be used for maintaining is temperature required, in the down-type fixed-bed reactor or up flow type fluidized-bed reactor under the reaction condition of pressure and space velocity.
Although these granular pattern carried catalysts (as be deposited on aluminium oxide or the silica supports cobalt-molybdenum or nickel-molybdenum) and the catalytic hydrogenation conversion process that adopts carried catalyst provide preferable effect for the hydrogenation and the hydro-conversion of coal and heavy oil feedstock, but some shortcomings of these granular pattern carried catalysts are, they are relatively poor with contacting of raw material, and because the rapid inactivation that pollution caused of the metal (as iron, titanium, nickel and vanadium) that coke laydown contains on catalyst and in the raw material.Equally, U.S. Patent No. 4,136,013 (Moll etc.) disclose a kind of emulsion-type metallic catalyst that is used for hydrogenation process, but it also has the shortcoming that catalytic activity is low, catalyst amount is high.Under the disclosed catalyst amount level of patent of Moll etc., the catalyst cost is too high, unless reclaim catalyst and reuse from unconverted raw material.U.S. Patent No. 4,077,867 and 4,134,825 (Bearden etc.) disclose the decentralized slurry attitude catalyst of the containing metal-carbon of original position formation, and this catalyst is called " M-Coke ", can be used for the hydro-conversion of coal, heavy oil and composition thereof.The catalyst of Bearden etc. is mainly based on molybdenum, and molybdenum than the iron costliness many.And, to the processing of the molybdenum catalyst after using also not as the iron catalyst after using is handled such environmental sound.U.S. Patent No. 4,486,293 (D.Garg) disclose the co-catalyst combination of a kind of iron and VI family or group VIII nonferrous metal, make the coal liquefaction of awarding in the hydrogen solvent with the water soluble salt of co-catalyst metal.Know, the catalyst that makes from the salt of water-soluble precursor usually can be under the coal liquefaction condition sintering, thereby can lose the required high degree of dispersion of high catalytic activity.U.S.A encloses patent No.5,168,088 (Utz etc.) disclose a kind of uniqueness pass through with iron oxide precipitation on the matrix of coal when improving in coal liquefaction the method for decentralized slurry attitude catalyst.But this deposition process of catalyst precipitation on whole coal raw material generally acknowledged it is very expensive for commercial-scale production.V.Pradhan etc. are at " catalysis of sulphation metal oxide in DCL/Direct coal liquefaction " (Catalysis in direct Coal Liquefaction by Sulfated Metal Oxides, Energy and Fuels, 1991, Vol.5) disclose the various disperse type catalyzers that can be used for the coal liquefaction process that have been found that in the literary composition, comprised sulphation transition metal oxide such as sulphation iron oxide (Fe
2O
3/ SO
4) and sulphation tin oxide (SnO
2/ SO
4), wherein add anion (SO
4 2-) effect be to prevent catalyst sintering or caking under the coal liquefaction condition.Yet for the catalyst that is used for various carbon raw material hydrotreatments, in particular for cheapness, environmental sound, the iron oxide based catalyst of highly active decentralized of catalytic hydrogenation conversion process, the form of catalyst and composition also need to do further improvement.
The invention provides fine granularity, iron oxide is slurry attitude catalyst main, high degree of dispersion, and this catalyst helps catalysis with the sulfate anion modification and with carbamate additives for low phosphorus, and it has high surface area and high hydrogenation and the hydrocracking of catalytic activity to improve carbon raw material.Catalyst is made by the hydroxide or the hydrogen peroxide oxidation compound of iron, and it is by at sulfate radical (SO
4 2-) anion exists to be settled out rapidly from saturated aqueous solution down and make, and help catalysis by the phosphorus (P) of adding low concentration, thereby make 100-250m is arranged after drying
2The fine-grained particles of the high surface of/g.It is sulfate radical (SO in solution that primary oxidation iron water from saturated solution becomes to be settled out
4 2-) carry out rapidly under the anionic existence, to make the fine granularity sediment of high surface.The catalyst precipitation thing preferably provides with gel or wet cheese formula and uses, and need not remove any wherein contained moisture from sediment.Yet, if wish to use the catalyst of dry powder form, then can filter, 100-120 ℃ of dry down and/or calcining under 450-550 ℃ to the catalyst precipitation thing, the primary particle size of catalyst precipitation thing is usually less than about 50 dusts, and secondary particle size is the 1-20 micron.For preferable gel that contains most of water or wet cake catalyst mode, the useful concentration range of iron is 5-20% (weight) in the final catalyst, the concentration range of sulfate anion is 0.5-10% (weight) in the final catalyst, and the concentration range of phosphorus catalyst is 0.05-2% (weight).The final fine granularity catalyst that dry back obtains should have 140-200m
2The high surface of/g.
Fine granularity of the present invention, anion-modified and phosphorus help the disperse type catalyzer composition of catalysis to can be used for various slurry attitude phase hydrogenation processing reaction, as the hydro-conversion that is used for carbon raw material (comprising coal, heavy crude residual oil, lignin and waste plastics material) is made required low boiling, the high additive value liquid hydrocarbon distillates product.Because these anion-modified and phosphorus help decentralized ferrum-based catalyst active high of catalysis, they can be used for above-mentioned various hydrogenation and hydroconversion reactions with lower concentration (with respect to 0.05-0.2% (weight) iron of raw material weight), and preferably can further react with heavy cut (more than 454 ℃) unconverted or that part the transforms Returning reactor that circulates again together.Because these decentralized fine granularity ferrum-based catalysts are to make from obtainable relatively inexpensive material, and its key component is the iron of environmental sound, therefore for extensive hydrogenation process, they are normally disposable and do not need to reclaim and regeneration.
The present invention advantageously provided fine-grained, anion-modified and phosphorus help catalysis, the iron oxide based catalyst of decentralized, this catalyst has high surface area and high catalytic activity.Catalyst makes easily, cheap, it can be used as disposable slurry attitude catalyst and is used for carbonaceous material (as coal, heavy crude residual oil and waste plastics) catalytic hydrogenation and hydroconversion process, to make required lower boiling liquid state and gaseous state hydrocarbon products.The present invention also comprises method for preparing catalyst and the hydroconversion process that makes required low boiling liquid hydrocarbon product with the decentralized ferrum-based catalyst.
The present invention also provides by be precipitated out the method for the above-mentioned catalyst of preparation rapidly from the aqueous solution in iron content, sulfate anion source and phosphorus source, and described method comprises the following steps:
(a) 20-30 ℃ down dissolving contain the iron of 5-20% weight and 0.5-10% weight sulfate anion molysite and contain the promoter metal salt of microcosmic salt, form the aqueous solution; With
(b) with the speed of 10-20 ml/min ammonium hydroxide is added in the described solution to form precipitation, final pH is 4.0-5.0.
In a preferable embodiment, initiation material is ferric sulfate pentahydrate Fe
2(SO
4)
35H
2O, the phosphorus source is phosphoric acid H
3PO
4, and the ammonium hydroxide that adds the 20-28% weight of capacity makes that pH is 4.0-5.0, thus the sediment of gel form formed.In this embodiment, preferred methods comprises the ammonium hydroxide of the 20-28% weight that adds capacity so that pH is 7.5-8.5, and filtering solution and 100-120 ℃ of following drying solution is 100-250m thereby make primary particle size less than 50 dusts and surface area
2The particle of/g.
In another preferable embodiment, initiation material is an ammonium ferric sulfate, and promoter metal salt is the phosphoric acid or the ammonium phosphate of 80% weight, and the Ammonia of the 20-28% weight of adding capacity is so that pH is 4.0-5.0, thus the sediment of generation gel form.In this embodiment, preferred methods comprises that it is 7.5-8.5 that the ammonium hydroxide of the 20-28% weight that adds capacity makes pH, filters then and at 100-120 ℃ of following dry sediment, is 100-250m thereby make less than 50 dusts and surface area
2The primary granule solid of/g.
Anion-modified disperse type catalyzer composition of the present invention comprises and sulfate radical (SO
4 2-) hydroxide and the hydrogen peroxide oxidation compound of iron of anion combination, it helps catalysis by adding carbamate additives for low phosphorus (P), with the active metal hydride as the fine granularity precipitated form.Catalyst is formed and is comprised that the iron of 5-20% (weight), sulfate anion and 0.05-2% (weight) phosphorus of 0.5-10% (weight) help catalytic metal, and all the other are the water that is at least about 60% (weight).Catalyst should use with wet cheese formula, and this wet cake is made up of precipitate particles gel in the water that contains 60-95% (weight) moisture, or is formed in the dry powder form that obtains behind drying and/or the calcining hydrogen peroxide oxidation compound sediment.In preferable gel form and occupation mode, the sediment that hydrolysis obtains need not filter or be dry, but directly uses with the form that makes.The catalyst gel form has significantly reduced the Catalyst Production cost, and can not lose it to the corresponding activity of hydrotreatment reaction at all.The secondary particle size of dried catalyst precipitation thing is the 1-20 micron, and surface area is 100-250m
2/ g.Preferable catalyst gel composition contains the iron of 8-16% (weight), the sulfate anion of 1-5% (weight) and the phosphorus of 0.5-1.5% (weight), and its surplus is a water.The scope of metal carrying capacity is to count the iron of 500-2000ppm (weight) and the phosphorus of 25-200ppm (weight) with respect to carbon raw material in the catalytic applications.Preferable metal carrying capacity is to count the iron of 800-1200ppm (weight) and the phosphorus of 50-150ppm (weight) with respect to raw material in hydroconversion reactions.
Decentralized iron oxide slurry attitude catalyst of the present invention is cheaply, and environmental sound is because its main component is an iron.These catalyst are very effective for the hydro-conversion of high-molecular-weight hydrocarbons, and these hydrocarbon comprise fossil fuel (as coal and heavy crude residual oil) and organic waste materials (as the mixed plastic in the MSW) and composition thereof.Catalyst of the present invention, no matter be preferable wet cake gel form or dry powder form, under the operating temperature of the Hydrogen Vapor Pressure of 5-20MPa, 400-460 ℃, the test under two sections pilot-plant productions of continuous type of 20 milliliters of high-pressure mini still reactors and 30 kg/day all is successful.The decentralized ferric oxide catalyst adopts haggles over little carrying capacity (0.05-0.2% (weight) iron) with respect to raw material, and they can one way (once-through) use in industrial hydro-conversion is produced like this.Independent use by decentralized slurry attitude catalyst of the present invention, and with being used in combination of other catalyst precarsor, change into liquid and gaseous products, lightweight distillate yield and at carbon raw material, all can obtain very good production performance aspect the hydrogen consumption of different material (comprising coal, petroleum residual oil, city waste plastics and lignin) when carrying out hydrotreatment.
The advantage of the catalyst of gel form is, when it added in high-temperature systems, the moisture in the gel is evaporation rapidly, and this helps the dispersion of catalyst granules, and makes the fragmentation of caking thing, thereby makes the interaction between particle-reactant more effective.It is that 400-460 ℃, hydrogen partial pressure are that 5-20MPa, raw material space velocity are 320-1280kg/h/m at temperature of reactor that phosphorus of the present invention helps the iron catalyst gel of catalysis can be used in particular for carbon raw material
3Carry out hydro-conversion under the broad operating condition of reactor volume.The suitable carrying capacity of disperse type catalyzer (with respect to the raw material meter) is that the iron and the phosphorus that is about 25-200ppm (weight) that is about 500-2000ppm (weight) in raw material weight can be provided.Adopt two sections backmixed reactor structures under these conditions, have the carbon raw material of 93-96% (weight) to be transformed, generate the lightweight fraction liquid of 60-73% (weight).Decentralized slurry attitude catalyst of the present invention tests successfully in 30 kg/day continuous type pilot-plants of coal (especially grizzle), heavy crude residual oil, waste plastics and composition thereof hydro-conversion.Usually,, there is the raw material that surpasses 95% (weight) to transform, generates the lightweight that surpasses 75% (weight) and can distillate product liquid for the two reactor structure that is with or without phase separation step between two sections.
Decentralized iron-based slurry attitude catalyst of the present invention has very high versatility in the hydrotreatment of the HMW carbonaceous material except that coal (as the mixed plastic in heavy crude residual oil, the MSW, biomass and lignin).Catalyst of the present invention than the active high key of disclosed other ferrum-based catalyst of document is, the fine size that they are initial, the surface area height, catalyst degree of scatter height, and they can keep the state of high degree of dispersion under reaction condition, these are the existence owing to anion-modified dose, and anion-modified dose of quilt generally acknowledged the sintering or the caking that can at high temperature prevent fine-grained particles.
Decentralized fine granularity ferric oxide catalyst of the present invention can be with a kind of preparation the in following two kinds of methods.Preferable method for preparing catalyst A has adopted 100 gram ferric sulfate pentahydrate Fe
2(SO
4)
35H
2O adds the phosphoric acid H of 9-17 gram 80% (weight) therein as initiation material
3PO
4, be dissolved in then in 150 ml waters.Speed with the 10-20 ml/min adds 60-70 milliliter 20-28% (weight) ammonium hydroxide (NH then
4OH), produce precipitation rapidly and form the sepia gel until at pH4.5 the time, gel contains 30% (weight) solid, and (the solid major part is Fe (OH)
3And FeOOH) and the phosphorus and the unhydrolysed molysite of sulfate anion modifier, precipitation.The gel that forms can be used for hydroconversion reactions and does not need further drying or purifying.The sulfate anion of the iron, 2.0% (weight) that gel that obtains from preparation method A or wet cake contain have an appointment 10% (weight) and about 1.0% phosphorus catalyst metal and water.
Preferable preparation method A catalyst can adopt the wet cheese formula that contains moisture that precipitates and obtain rapidly by particle before filtration and drying precipitated particle when being used for hydroconversion process, or adopt the fine granularity anhydrous powder form of drying.For the final catalyst made from wet cake or gel form, when being about 4.0-4.5, ends pH by in molysite, adding the hydrolysis that 20-28% (weight) ammonium hydroxide takes place.The gel catalyst of this method A can advantageously be used for the hydrogenation liquefaction of bituminous coal and ub-bituminous coal with wet cake (gel) or dry powder form, to prepare required liquid hydrocarbon product, and, no matter adopt the catalyst of which kind of form, the catalyst of method A all shows similar positive-effect to the catalytic activity of course of reaction.Therefore, for all kinds of hydroconversion reactions, the catalyst filter cake that contains 20-50% (weight) solid is more more economical than the beaded catalyst of drying, because this class dispersed catalyst is set under low concentration or the carrying capacity (with respect to coal raw material meter), and the moisture that contains in the catalyst is safe from harm to course of reaction.The method A of drying slurry attitude catalyst contains the iron of the 8-30% that has an appointment (weight) at least, the have an appointment iron of 12-25% (weight) of preferable containing.When method A catalyst helped catalysis with carbamate additives for low phosphorus, the concentration of phosphorus was about 0.05-2% (weight), sulfate radical (SO
4) anionic content is 2-6% (weight).The BET surface area is at 140-200m
2Between/g.
For method B Preparation of catalysts, adopt ammonium ferric sulfate (being also referred to as iron (III) alum) Fe
2(SO
4)
3(NH
4)
2SO
4.24H
2O is as initiation material.Catalyst is by being prepared as follows, and at first 100 gram iron (III) alum is dissolved in the 100-150 ml water, adds the Ammonia of 20-28% (weight) with the speed of 10-20 ml/min, to generate Fe (OH) when final pH is 7.5-8.5
3Deposit seed (hydrolysis by initial molysite obtains).Washing precipitation particle, filtration and about 100-120 ℃ dry 20-24 hour down.If desired, also can be at the about 450-550 ℃ of following further iron oxide sulfate catalyst of the drying that obtained in 24 hours of calcining, thus be the hydrogenation cracking activity that cost improves catalyst with the loss hydrogenation activity.In the catalyst of drying, add phosphoric acid (H
3PO
4) as the source of phosphorus catalyst, after drying, to make Fe (OH)
3/ SO
4/ P catalyst.
No matter the decentralized ferrum-based catalyst is to use with gel or with wet cheese formula, and the catalyst that method A or method B make all need mix with slurry oil (circulating solvent in the coal liquefaction process) under being lower than the temperature of water boiling point in advance.The catalyst of dry powder form can add in the raw material mixing channel simply, and the stirring of suitable mode is provided.Also must there be enough sulphur in original position sulfuration for dispersed catalyst in the reaction system; Sulphur can provide by raw material, or form that can sulfur-containing compound adds in the reaction system.
Use the course of reaction of disperse type catalyzer of the present invention and described with reference to following accompanying drawing, wherein:
Fig. 1 is the schematic flow sheet of the catalysis two-stage hydrogenation conversion process that is tightly linked, all adopts decentralized iron-based slurry attitude catalyst in two sections reactor;
Fig. 2 is and the similar schematic flow sheet of Fig. 1 that different is to adopt decentralized iron-based slurry attitude catalyst in first section reactor, and adopts the fluid bed of granular pattern carried catalyst in second section reactor;
The graphical presentation of Fig. 3 adopts the comparison of coal conversion ratio behind the different disperse type catalyzers, petroleum residual oil conversion ratio and distillate yield for the ub-bituminous coal raw material in the continuous type pilot-plant is produced; With
The graphical presentation of Fig. 4 adopts the comparison of gasoline fraction yield behind the different disperse type catalyzers, gas yield and hydrogen consumption for the ub-bituminous coal raw material in the continuous type pilot-plant is produced.
Fine granularity decentralized ferric oxide catalyst of the present invention can be advantageously used in various HMW carbon raw materials The catalytic hydrogenation of (comprising coal, petroleum residual oil, plastic wastes and composition thereof) transforms, to make required low boiling The point liquid hydrocarbon product, these products comprise the vehicles and government utility fuel, as gasoline, diesel oil, kerosene, Fuel oil and petroleum chemicals. No matter catalyst of the present invention is better gel form or drying Particle form all can add in the hydrocarbon feed of reactor upstream, or can be under HTHP and the slurry oil of premix Together in the direct injecting reactor. For making the disperse type catalyzer metal reaction in-situ activation that cures, reactor system In the system enough sulphur or hydrogen sulfide must be arranged. Usually, the amount of the sulphur that provides should be in the gas phase of hydrogen hydro-conversion approximately The H that contains 5-10% (weight)2S。
Adopt the catalytic hydrogenation conversion process of catalyst of the present invention in the single hop reactor, to carry out, but preferably adopt With the two-stage hydrogenation conversion reactor of series connection, the arrangement or two that can closely link to each other of these two reactors intersegmentally has one Individual gas/liquid intermediate separator. For adopting anion-modified, iron oxide catalysis that phosphorus helps catalysis of the present invention The hydroconversion process of agent, carbon raw material should contain the sulphur of capacity so that catalyst full cure when operation. When When the sulphur that feed stream contains is in shortage, should adds sulfur-containing compound in the feed stream or directly add first paragraph and react In the device. For two reactor, can keep different reaction conditions in each reactor, this be make specific It is best desired that the effect of hydrocarbon feed hydro-conversion reaches. As shown in Figure 1, first paragraph and second segment reactor In all can only contain decentralized slurry attitude catalyst.
Two reactor all can operate under the temperature in the basic 400-460 ℃ of scope that equates, or first paragraph Temperature of reactor can be below or above the temperature of second segment reactor. Yet usually preferably, first paragraph is anti-Answer actuator temperature to hang down 10-30 ℃ than the temperature of second segment reactor. Distillate to the first paragraph reactor divides mutually From, also carry out therein removing before the further catalytic reaction so that flow into the second segment reactor at the heavy liquid fraction Gas and lightweight fraction.
Perhaps, as shown in Figure 2, the mode that catalyst can mix is used, and one of them reactor is (best The second segment reactor) (cobalt-molybdenum or the nickel-molybdenum that support such as lead oxide are squeezed into can to contain the granular pattern carried catalyst The type catalyst) catalyst bubbling bed. The hydroconversion reactions device of two segmentations all operates in the back-mixing mode. Liquid reactor and catalyst slurry can be in inside reactor or outer loop, so that catalyst/liquid wherein fills Branch mixes and contacts. For the arrangement of Fig. 2, two reactors can be roughly the same in 400-460 ℃ of scope Operate under the temperature. Yet the temperature ratio that usually is preferably the first paragraph reactor contains the granular pattern carried catalyst The second segment reactor low 10-30 ℃.
Effluent stream to the first paragraph reactor is separated, in order to form steam and liquid fraction, to obtaining Liquid fraction distill, distillate product to generate all kinds of required low boiling liquid hydrocarbons. Usually will contain big The heavy liquid residual oil circulation of the destilling tower of part disperse type catalyzer bottom is returned in the first paragraph reactor, with at it In carry out further hydro-conversion.
As shown in Figure 1, the carbon raw material (such as particulate coal) that provides with suitable slurry oil (slurrying oil) and 10 places Form slurry, pressurization, and and the hydrogen one that provides of the decentralized ferrum-based catalyst that provides of 11 places and 12 places Play upwards to enter in the first paragraph reactor 14, the reactant in the first paragraph reactor 14 13 place's back-mixings and in Section's circulation is to produce continuously stirred tank reactor (CSTR) (CSTR) effect. Better reaction condition is that temperature is 410-430 ℃, hydrogen partial pressure is that 7-17MPa and space reactor speed are 400-800kg/h/m3 If carbon raw material institute The sulphur deficiency that contains is so that catalyst full cure in reactor, can be at the 10a place with suitable sulfur-containing compound (as Hydrogen sulfide) add in the feed stream 10.
The effluent from the partial reaction of first paragraph reactor at 15 places can add at 16 places the hydrogen that replenishes, 18 places add the catalyst that replenishes, and enter the second segment reactor 20 at 19 place's back-mixings, to advance therein one Step reacts. Better operating condition is that temperature is 420-450 ℃ in the reactor 20, and hydrogen partial pressure is 7-17MPa. Effluent stream flows out from 21, and at the position 22 a series of high pressure and the low-pressure gas-liquid that provide Be further processed in separator and the distilation steps. Comprise C1-C
3Light hydrocarbon gas and H2、CO、CO
2、
NH
3And H2The product gas stream of S is from 23 discharges, and purifying obtains the hydrogen cut and provides with 16 places as required Hydrogen make-up return the first paragraph reactor in 12 places circulations together. Boiling spread is generally 80-750 °F liquid The attitude hydrocarbon products is discharged from 24. Contain the heavier liquid more than 750 °F or the silt of some disperse type catalyzers Slurry stream 25 as liquid stream 26 circulations return first paragraph reactor 14, and part high-melting-point product and anyly do not react Solid can be used as liquid stream 27 and remove. If need, it is solid that the liquid product stream at 24 places can flow into online catalysis Fixed bed hydrotreater 28 is to improve the quality that distillates product from 29 lightweights of discharging.
The another kind of process that has shown the two-stage catalytic hydrogenation conversion of carbon raw material (such as coal) among Fig. 2. This Fig. 2's Process and similar process shown in Figure 1, its first paragraph reactor 14 is same to adopt decentralized slurry attitude of the present invention Catalyst. Yet the first paragraph reactor effluent at 15 places enters two sections intermediate gas-liquid high pressure separator 30, in separator 30, remove devaporation fraction 31, and liquid/slurry fraction 32 and the hydrogen that adds at 34 places Enter together in the second segment reactor 40, traditional carried catalyst that is squeezed into is arranged in the second segment reactor 40 Expanded bed 42. For the coal raw material, the temperature of first paragraph reactor is than second segment reactor in Fig. 2 arranges The high 10-30 of temperature ℃. The temperature of first paragraph reactor 14 is preferably 420-450 ℃, the second segment reactor catalysis The temperature of bed is preferably 410-430 ℃. The fine granularity disperse type catalyzer that contains in the liquid distillate stream 32 has passed through the Catalyst expanded bed 42 in the second stage reactor 40, expanded bed is by circulation process downspout 43 and pump 44 Liquid reactor expands. The effluent stream 41 of second segment reactor enters product separation position 46, this one The position is similar to the method for operating of separated part 22 in Fig. 1 process. Product gas stream is discharged heavy hydrocarbon from 47 / slurry flow is from 48 discharges, and it may contain some from the disperse type catalyzer of first paragraph reactor 14, It is circulated to reactor 14 by the same way as in Fig. 1 process.
The part of slurry flow 48 can be discharged at 49 places. For the process shown in Fig. 1 and Fig. 2, boiling point is logical The light liquids product stream 50 (process distillates product only) of being everlasting between 80-750 °F can add by online fixed bed Hydrogen device 52 is so that the product that distillates that 54 places obtain has higher hydrogen content and lower hetero atom (N, S, O) Content.
Decentralized ferric oxide catalyst of the present invention also can be advantageously used in the hydro-conversion of petroleum residual oil raw material, with And the cracking of HMW polymerization raw material, these polymer raws for example are the waste plastics from MSW, Comprise polyethylene, polypropylene and polystyrene, they provide with independent blend state, or with coal and/or heavy Oil provides after mixing. The suitable reaction condition of these petroleum residual oil hydroconversion reactions is that temperature is 425-450 ℃, hydrogen partial pressure is 7-17MPa. The suitable reaction condition of waste plastics hydrocracking and coal and heavy crude slag The reaction condition of oil hydrocracking is identical.
Decentralized ferric oxide catalyst of the present invention be successfully used to altogether refining of DCL/Direct coal liquefaction, coal/oil, coal/ Altogether refining of waste plastics, heavy oil modification, oil/waste plastics refines altogether and coal/oil/waste plastics refines the continuous pilot-plant of process altogether In the production. Adopt the aforesaid operations condition, the operating characteristics of processing procedure has significantly to be improved, not only petroleum residual oil Conversion ratio and product of distillation yield increase, and the operation of process is also comparatively easy, because carrier model catalysis Agent ebullated bed type reactor is replaced by better simply back-mixing formula slurry attitude hydrogen-catalyst reactor. The catalysis of decentralized slurry attitude The application of agent is also so that reaction raw materials can utilize space reactor better, so the total output of processing procedure can be carried Up to 50%.
The present invention further describes with reference to the following example, but these embodiment should not be considered to limit this
Scope of invention.
In order to estimate the effect of phosphorus reactive metal in the decentralized ferric oxide catalyst, with ub-bituminous coal (WyomingBlack Thunder Mine) as raw material, continuous type two-stage hydrogenation in 30 kg/day transforms in the pilot-plant, adopt molybdenum as the anion-modified decentralized ferric oxide catalyst of reactive metal with contain the same ferric oxide catalyst of phosphorus, compare test as the co-catalyst material.Operating condition, be listed in the following table 1 with respect to catalyst loading and these result of the tests of raw material.
Table 1
Decentralized iron oxide molybdenum catalyst gel and iron oxide phosphorus
The catalyst gel compares for the result of ub-bituminous coal liquefaction
The decentralized iron oxide urges the decentralized iron oxide to urge
It is phosphorous that the process condition agent contains the molybdenum agent
Space velocity, kg/h/m
3Reactor
First section 876 898
Second section 876 898
Temperature of reactor, ℃
First section 441 441
Second section 450 449
Pressure, MPa 17 17
The catalyst metals carrying capacity, ppm
Iron 5,000 1000
C
1-C
3Gas 9.0 9.9
Gasoline fraction (C
4-117 ℃) 23.2 20.3
Middle distillate (177-343 ℃) 23.2 25.6
Heavy fraction (343-524 ℃) 15.6 21.3
Residual oil (more than 524 ℃) 10.0 4.1
Hydrogen consumption 5.8 6.7
Coal conversion ratio 92.8 93.4
Bottoms conversion 82.6 89.3
C
4-343 ℃ of fraction yield 46.4 45.9
C
4-524 ℃ of fraction yield 62.0 67.2
Hydrogen efficient 10.7 10.0
C
4-524 ℃ of fraction yields (bucket of unit ton coal) 3.5 3.8
From The above results as can be seen, add coal and bottoms conversion and the C that the decentralized iron catalyst of 100ppm phosphorus reactive metal provides
4-524 ℃ of cut yield are than only as the ferric oxide catalyst of the sulfate anion modification of reactive metal raising being arranged all with molybdenum.
Shown also among Fig. 3 and Fig. 4 that sulfate radical modification of the present invention, phosphorus help the ferric oxide catalyst of catalysis and the comparative result that helps the same catalyst of catalysis without phosphorus.As can be seen, phosphorus of the present invention helps the disperse type catalyzer of catalysis to make hydrogen consumption and distillate yield higher, especially to the mode of operation of residual oil complete alternation.
In two sections experimental provisions of 30 kg/day continuous types, No. 6 bituminous coal raw materials of Illinois are adopted contain 100ppm (weight) phosphorus, contain or do not contain molybdenum, anion-modified, decentralized ferric oxide catalyst compares test.Operating condition, with respect to the catalyst loading of coal and the results are shown in the following table 2.
Table 2
The disperse type catalyzer operation of bituminous coal liquefaction
Operating condition
Space velocity, fresh feed amount/reactor volume, Pounds Per Hour/cubic feet reactor
First section 38.5 42.2
Second section 38.5 42.2
Temperature of reactor, ℃
First section 444 447
Second section 474 458
Reactor pressure, MPa 17 17
The disperse type catalyzer carrying capacity, ppm
Iron 1,000 1000
Proofread and correct the back net yield, the anhydrous ashless fresh feed of % (weight)
C
1-C
3Gas 7.2 6.7
Gasoline fraction 19.2 18.4
Middle distillate 32.6 32.3
Heavy fraction 21.4 22.7
Residual oil 10.3 11.0 more than 524 ℃
The operating characteristics of unconverted raw material 4.4 3.8 processing procedures, the anhydrous ashless fresh feed of % (weight)
Hydrogen consumption 5.52 5.23
Total raw material transforms and (does not contain SO
3) 95.6 96.2
Residual oil transforms 85.3 85.3 more than 524 ℃
C
4-524 ℃ of fractions 73.2 73.4
From The above results as can be seen, the bituminous coal feedstock conversion becomes C
4-524 ℃ of cuts and more than 524 ℃ the percentage conversion of residual oil fraction be basic equating, this shows that the phosphorus that adds in the catalyst is than the prior component of molybdenum that adds.
In two sections hydrogenation apparatus, adopt phosphorous decentralized ferric oxide catalyst to carry out several times continuous type and refine test altogether the raw mix of various ub-bituminous coals, petroleum residual oil, automobile organic waste materials and mixed waste plastic.Operating condition and the results are shown in the table 3.
Table 3
The catalysis of coal/petroleum residual oil raw material and automobile organic waste materials and/or waste plastics is refined altogether
Operating condition
Raw material is formed, % (weight)
Coal (Black Thunder Mine) 100 0 50 75 50
Waste plastics 0000 25* space velocities, pound fresh feed/inch/cubic feet reactor volume
First section 44.9 39.6 37.5 39.5 33.4
Second section 44.9 39.6 37.6 39.5 33.4
Temperature of reactor, ℃
First section 441 442 441 443 441
Second section 449 451 451 452 450
Pressure, MPa 17 17 17 17 17
The disperse type catalyzer carrying capacity, ppm
Iron 1,000 1,000 1,000 1,000 1000
C
1-C
3Gas 9.9 7.0 8.6 6.9 7.8
Gasoline fraction 20.3 21.4 25.5 14.7 20.7
Middle distillate 25.7 23.0 22.8 16.6 19.5
Heavy fraction 21.6 24.7 18.5 25.4 21.2
Residual oil 3.7 16.0 10.5 18.0 14.0 more than 524 ℃
The operating characteristics of unconverted coal 6.8 3.6 6.0 9.6 8.9 processing procedures, the anhydrous ashless fresh feed of % (weight)
Raw material reclaims balance 100.8 100.6 102.7 102.9 104.1
Hydrogen consumption 6.7 5.9 6.4 6.1 3.2
Coal conversion ratio (not containing SO) 93.4 95.9 94.6 90.9 91.7
The conversion ratio 89.3 80.4 83.9 73.8 77.8 of fraction more than 524 ℃
C
4-524 ℃ of fractions 67.2 69.5 67.5 57.5 61.6
The residual thing yield 4.1 15.6 10.7 17.1 13.8 of heating up in a steamer more than 524 ℃
* 60% high density polyethylene (HDPE) and 40% polystyrene
The result of these tests shows, adopt the decentralized ferric oxide catalyst of phosphorous reactive metal of the present invention can obtain high percentage conversion and preferable liquid product of distillation yield, catalyst of the present invention is to be used for the effective catalyst of the rudimentary ub-bituminous coal of common refining and heavy crude residual oil and debirs (comprising automobile organic waste materials and mixed waste plastic).
Claims (22)
1. a decentralized, fine granularity, anion-modified and phosphorus help the slurry attitude catalyst of catalysis, and this catalyst is by 0.5-10% weight percent sulfuric acid root SO
4 2-Anion, hydroxide or hydrogen peroxide oxidation compound sediment, the phosphorus catalyst of 0.05-2.0% weight and the water of its surplus of counting the iron of 5-20% weight with iron are formed, and the primary particle size of this catalyst is less than 50 dusts, and secondary particle size is the 1-20 micron.
2. catalyst according to claim 1, wherein said slurry attitude catalyst contain hydroxide or the hydrogen peroxide oxidation compound sediment of counting the iron of 8-16% weight with iron, the sulfate radical SO of 1-5% weight
4 2-The phosphorus of anion and 0.5-1.5% weight, its surplus are water.
3. catalyst according to claim 1, wherein sediment is the gel form that contains the water of at least 60% weight.
4. catalyst according to claim 1, wherein sediment is that surface area is 100-250m
2The fine-grained particles form of the drying of/g.
5. a decentralized, fine granularity, anion-modified and phosphorus help the slurry attitude catalyst of catalysis, and this catalyst is by 1.0-5.0% weight percent sulfuric acid root SO
4 2-Anion, hydroxide or hydrogen peroxide oxidation compound sediment, the phosphorus catalyst of 0.5-1.5% weight and the water of its surplus of counting the iron of 8-16% weight with iron are formed,, described sedimentary primary particle size is less than 40 dusts.
6. one kind by being precipitated out the method for preparing the described catalyst of claim 1 rapidly from the aqueous solution in iron content, sulfate anion source and phosphorus source, and described method comprises the following steps:
(a) 20-30 ℃ down dissolving contain the iron of 5-20% weight and 0.5-10% weight sulfate anion molysite and contain the promoter metal salt of microcosmic salt, form the aqueous solution; With
(b) with the speed of 10-20 ml/min ammonium hydroxide is added in the described solution to form precipitation, final pH is 4.0-5.0.
7. method for preparing catalyst according to claim 6, wherein initiation material is ferric sulfate pentahydrate Fe
2(SO
4)
35H
2O, the phosphorus source is phosphoric acid H
3PO
4, and the ammonium hydroxide that adds the 20-28% weight of capacity makes that pH is 4.0-5.0, thus the sediment of gel form formed.
8. method for preparing catalyst according to claim 7, comprise the ammonium hydroxide of the 20-28% weight that adds capacity so that pH is 7.5-8.5, filtering solution and 100-120 ℃ of following drying solution is 100-250m thereby make primary particle size less than 50 dusts and surface area
2The particle of/g.
9. method for preparing catalyst according to claim 6, wherein initiation material is an ammonium ferric sulfate, promoter metal salt is the phosphoric acid or the ammonium phosphate of 80% weight, and the Ammonia of the 20-28% weight of adding capacity is so that pH is 4.0-5.0, thus the sediment of generation gel form.
10. method for preparing catalyst according to claim 9, it is 7.5-8.5 that the ammonium hydroxide that comprises the 20-28% weight that adds capacity makes pH, filters then and at 100-120 ℃ of following dry sediment, is 100-250m thereby make less than 50 dusts and surface area
2The primary granule solid of/g.
The process of preparation low boiling liquid hydrocarbon product 11. a HMW carbon raw material catalytic hydrogenation is converted, described process comprises the following steps:
(a) be 750-860 temperature, hydrogen dividing potential drop, the 320-1280kg/h/m that 5-20MPa is 735-2950psig at 400-460 ℃
3Be 20-80lb/h/ft
3Space reactor speed under, make the described dispersion anion-modified ferrum-based catalyst reaction of carbon raw material and claim 1, catalyst is the iron of 500-2000ppm with respect to raw material and makes catalyst vulcanization in the presence of capacity sulphur, contains the reaction effluent of vapour-liquid phase cut with generation; With
(b) effluent is separated into gas and liquid distillate, the distillating liquid cut, and take out the low-boiling point liquid hydrocarbon products.
12. catalytic hydrogenation conversion process according to claim 11, wherein carbon raw material is a coal, and reaction condition is that temperature is that 425-450 ℃, hydrogen dividing potential drop are that 7-17MPa, space velocity are 400-800kg/h/m
3Reactor volume.
13. catalytic hydrogenation conversion process according to claim 11, wherein raw material is a heavy crude residual oil.
14. catalytic hydrogenation conversion process according to claim 11, wherein raw material is the mixture of coal and heavy crude residual oil.
15. catalytic hydrogenation conversion process according to claim 11, the wherein mixed waste plastic formed by polyethylene, polystyrene and polypropylene of raw material.
16. catalytic hydrogenation conversion process according to claim 11, wherein raw material is the mixture of heavy crude residual oil and waste plastics.
17. catalytic hydrogenation conversion process according to claim 11, wherein raw material is the mixture of coal, mixed waste plastic and heavy crude residual oil.
18. catalytic hydrogenation conversion process according to claim 11, wherein raw material reacts in the catalytic reactor of two sections couplings of series connection.
19. catalytic hydrogenation conversion process according to claim 11, wherein raw material reacts in the two reactor of series connection, and the middle separating step of gas-liquid is arranged between two reactors.
20. catalytic hydrogenation conversion process according to claim 18 wherein has the decentralized ferric oxide catalyst in first section reactor, and the expanded bed of extrusion modling carried catalyst is arranged in second section reactor.
21. catalytic hydrogenation conversion process according to claim 18, wherein the temperature of first section reactor is hanged down 10-30 ℃ than the temperature of second section reactor.
22. catalytic hydrogenation conversion process according to claim 20, wherein the temperature of first section reactor is than the high 10-30 of temperature ℃ of second section reactor.
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| CN98122746A CN1107540C (en) | 1998-11-30 | 1998-11-30 | Dispersion anion-modified and phosphorus supporting ferric oxide catalyst |
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| US8123933B2 (en) * | 2008-06-30 | 2012-02-28 | Uop Llc | Process for using iron oxide and alumina catalyst for slurry hydrocracking |
| US20120016167A1 (en) * | 2010-07-15 | 2012-01-19 | Exxonmobil Research And Engineering Company | Hydroprocessing of biocomponent feeds with low pressure hydrogen-containing streams |
| TWI414592B (en) | 2010-11-05 | 2013-11-11 | Ind Tech Res Inst | Method for refining oil |
| CN102465004B (en) * | 2010-11-10 | 2014-12-24 | 财团法人工业技术研究院 | Method for modifying oil product |
| CN104549276B (en) * | 2013-10-28 | 2017-04-26 | 中国石油化工股份有限公司 | Thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof |
| WO2016009333A1 (en) | 2014-07-17 | 2016-01-21 | Sabic Global Technologies B.V. | Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972829A (en) * | 1974-11-07 | 1976-08-03 | Universal Oil Products Company | Method of depositing a catalytically active metallic component on a carrier material |
| US4486293A (en) * | 1983-04-25 | 1984-12-04 | Air Products And Chemicals, Inc. | Catalytic coal hydroliquefaction process |
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1998
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972829A (en) * | 1974-11-07 | 1976-08-03 | Universal Oil Products Company | Method of depositing a catalytically active metallic component on a carrier material |
| US4486293A (en) * | 1983-04-25 | 1984-12-04 | Air Products And Chemicals, Inc. | Catalytic coal hydroliquefaction process |
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