CN1464031A - Coal tar hydrogenation process and catalyst therefor - Google Patents
Coal tar hydrogenation process and catalyst therefor Download PDFInfo
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Abstract
The present invention, coal tar hydrogenating process and catalyst, has obvious economic and environment protecting significance. Different hydrogenating catalysts are developed for meeting the requirement of hydrogenating coal tar of different components. The hydrogenating reactor has inlet pressure not higher than 15.0 MPa. After coal tar is hydrogenated in proper process to modify, may be obtained high-quality naphtha, high-quality diesel oil component or diesel oil, high-quality needle coke material and high-purity chemical product. The key point of the present invention is to use the developed special hydrogenating refining and modifying catalyst in hydrogenating coal tar.
Description
The technical field this patent belongs to coal chemical technology, relates to a kind of novel coal tar hydrogenation process and catalyzer.Reasonable utilization to coal tar is especially significant to environment protection.Its essence is hydrogenation technique based on refining of petroleum, by engineering development, research special-purpose catalyst, the excellent good fuel of component production environment or the petrochemical materials of environmental pollutions such as the desulfurization of realization coal tar, denitrogenation.
Background technology coal tar is one of product of the dry distillation of coal and coal generating gas.The deep processing of coal tar is method of hydrotreating especially, once receives much attention and drops into substantial contribution and manpower studies in twentieth century 50, the sixties.Because China finds and the recovery of subterranean oil that on grand celebration, Xinjiang and other places petroleum products is as the very fast motor spirit that has replaced gelatin liquefaction, vaporization to produce of main energy sources.From twentieth century seventies, China almost nobody shows any interest in the research and development that coal tar deep processing is produced the liquid product of high-quality environment-friendly type.Until twentieth century end of the nineties, because the raising of the raising of environmental consciousness, oil Refining Technologies, people be to the raising of the understanding of petroleum resources, the comprehensive utilization of coal is paid attention to by the knowledgeable people again.Republic of South Africa is because the racial discrimination problem is sanctioned by countries in the world for a long time, and South Africa is keeping rank first always aspect the processing of coal.But south african patent had not been found in the patent inquiry.Japan comparatively payes attention to the research of coal processing owing to the scarcity of petroleum resources always.Up to twentieth century the mid-80, Japan is still relevant for the research of coal processing and patent application is arranged, but the industrial implementation situation rarely has report.1985 07 month 22 Japanese Patents<application number〉method of hydrotreating of 85105609 coal-tar pitches, its objective is under the mild hydrogenation condition the refining back of coal-tar pitch is produced carbonaceous material.1985 Japanese Patent (application number 85107441) to coal tar hydrogenation process and catalyzer, the coal tar coking process has a detailed description.It is to produce high-quality needle coke that this Japanese Patent adopts the main purpose of method of hydrotreating reconstructed coal tar; its catalyst activity component is an active metal component with the metallic sulfide of VIII such as molybdenum, nickel, cobalt and VIB; but do not adopt titanium dioxide carrier and non-metal assistant; do not mention also in the technical process that full cut adopts the switch protecting reactor technology without pretreated coal tar, and hydrogenator inlet hydrogen dividing potential drop is 15.0MPa.This Japanese Patent has lost patent protection power in 1989.
At present, the required coke major part of domestic steel-making enterprise is from coal, and process of coking also can produce tar.There is vaporization factory in domestic many cities, but also different according to the different by-product coal tar of the tar content oil mass of coal, coal tar output is more in the vaporization factory below 50,000 tons/year.The coal tar part of these coking plants and vaporization factory by-product is directly burnt as low-quality fuel oil behind acid-alkali refining, or directly burn as emulsion fuel after the emulsification, impurity such as contained sulphur, nitrogen become sulphur and nitrogen oxide in combustion processes discharges into the atmosphere and causes topsoil, and the acid-alkali refining process produces large amount of sewage again; A part is behind acid-alkali refining, and extraction separation goes out phenol, burnedly after the chemical substances such as naphthalene fall or as pipeline anti-corrosive paint, water-proof material, and the subsidiary material of porcelain gloss firing etc., technical economic benefit is relatively poor, and causes than serious environmental and pollute.In addition, coal resources in China is abundanter, except that coking and gas making, also has a large amount of coals directly to be burnt as heating and culinary art by people.Impurity such as the contained sulphur of coal, nitrogen becomes sulphur and nitrogen oxide and discharges into the atmosphere and cause topsoil in combustion processes like this, and coal combustion process also causes dust pollution.Therefore, be that the raw material production town gas is more and more higher as the ratio of domestic fuel with the coal, the coal tar oil mass of association simultaneously also rolls up.And the China's oil inadequate resource, the crude oil import ratio increases year by year.With coal tar is stock oil, adopts more suitable secondary processing means to produce clean fuel or the petroleum products suitable with petroleum products, not only has remarkable economic efficiency, also has obvious social simultaneously.The technician of Shanghai Boshen Engineering Technology Co., Ltd. is with the working experience and the responsive technology consciousness of for many years petrochemical industry, domestic and international present situation is carried out analysis-by-synthesis, after carrying out scientific forecasting future, coal tar hydrogenating is produced environmentally friendly machine carry out the integrated technology exploitation, invented novel coal tar hydrogenation process and catalyzer proprietary technology.
Summary of the invention the present invention compares with Japanese Patent has following advantage: can change setting or the switch protecting reactor is not set according to raw material in the described technical process of this patent, can adopt form reactors such as ebullated bed.Hydrogenator inlet hydrogen dividing potential drop of the present invention is not more than 15.0Mpa.Special-purpose hydrogenation pre-refining catalyzer of the present invention and catalyst for hydro-upgrading active ingredient and carrier and Japanese Patent are incomplete same, and be active high behind the adding auxiliary agent, therefore, can reduce the pressure of hydrogenation reaction.Hydrogenated products not only can the production high added value needle coke, can also production high-quality petroleum naphtha, fine-quality diesel oil or fine-quality diesel oil blending component.The objective of the invention is with resource rational utilization and environmental protection is target, utilizes petroleum refining industry's modern technologies to yield products of quality with coal tar to the transplanting of the coal manufacture field property improved, and reduces the hydrogen dividing potential drop of hydrogenation reaction.Improve the quality of coal tar, the protection environment.
Key of the present invention is an engineering, as: suspension bed technological development etc.; The research and development of supporting catalyzer.Utilize existing various hydrogenation technique technology, utilize new catalytic material and auxiliary agent to develop special-purpose hydrofining and catalyst for hydro-upgrading, realize the final purpose of coal tar hydrogenating.
The cardinal principle of this patent (Fig. 1, Fig. 2) is described below:
The key distinction of Fig. 1, technical process shown in Figure 2 is the reactor types difference, and 13 is fixed-bed reactor among Fig. 1, and its quantity is 1 to 10.13 is suspension bed or moving-burden bed reactor among Fig. 2, and its quantity is 1 to 5.Below be described in detail the technical process of this patent.The described coal tar 1 of this patent enters preliminary fractionator 10 and removes less than C5 fraction 2, and this cut acts as a fuel or mixes the back with product fractionation cat head less than C5 fraction 2 and produce butagas and No. six high value added products such as extract oil.Preliminary fractionator 10 can fractionate out raw naphtha cut 3, gas oil fraction 4 and crude asphalt 5 and carry out hydrogenation respectively, also can mix or carry out hydrogenation 5 respectively and go out device, as pipeline anti-corrosive paint, water-proof material, with coal mixing gas making etc. as pitch blend component or comprehensive utilization with 3 and 4.Preliminary fractionator 10 also can only fractionate out 2,3,4,5 not in fractionation as flashing tower, and 3,4,5 mixture enters switch protecting reactor 11,12 from the extraction of 10 bottoms and removes iron and other solid impurity.11,12 periodic replacement catalyzer switch use.11, the raw material behind 12 pre-refinings 9 is mixed into hydrogenator 13 separately and/or with hydrogenation unconverted oil 8.The reaction product of reactor 13 enters product separation column 14, fractionates out high-quality petroleum naphtha 6, fine-quality diesel oil or fine-quality diesel oil blending component 7, unconverted oil 8.If when 13 charging was raw naphtha 3 or gas oil 4,14 did not only produce unconverted oil for flashing tower.Can be used as the CONTINUOUS REFORMER raw material behind the impurity such as the 6 further desulfurization of high-quality petroleum naphtha, arsenic, or directly as fine cracking of ethylene raw material, produce special solvent etc. after also can extracting the benzene hydrocarbon class.Unconverted oil 8 can go out device and mix with other cut and produce needle coke and also can enter hydrogenator 13 with raw material 9 mixed cycle behind 11,12 pre-refinings and further transform.
This patent is owing to require to have special-purpose catalyzer behind the engineering development.According to coal tar nitrogen, the characteristics that iron level is high require catalyzer will have two kinds at least, and promptly the pre-refining catalyzer has higher denitrogenation and deferrization ability, and modifying catalyst has certain cracking ability.The pre-refining catalyzer is made the filling of classification from top to bottom in reactor of different pore volumes and shape according to processing requirement, and its shape can be sphere, microballoon, bar shaped, belt, wheel shape, cylinder, trifolium etc.The mixture that hydrogenation pre-refining catalyzer adds with aluminum oxide behind the titanium oxide of 1%--40% (mass percent) is made carrier, is active metal component and adds VA family and/or some non-metallic element of VIIA family is an auxiliary agent with the metallic sulfide of VIII such as molybdenum, nickel, cobalt and VIB.Its manufacturing side adopts saturated spray or saturated pickling process.Its compositing range and physico-chemical property see Table 1.
The purpose of this patent special-purpose catalyst development is to satisfy processing requirement, reduces hydrogenation reaction hydrogen dividing potential drop, thereby reduces the one-time investment that hydrogenation unit is built.
Table 1 hydrogenation pre-refining catalyzer physico-chemical property
Title | Coal tar hydrogenating pre-refining catalyzer |
Chemical constitution, % (quality) | |
MoO 3 | 5.0-20.0 |
NiO | 1.0-10.0 |
P | 0.1-5.0 |
| 1%-40% |
Al 2O 3 | Surplus |
Physical properties | |
Specific surface, m 2/g | 70-260 |
Pore volume, ml/g | 0.20-0.80 |
Crushing strength, N/cm | ≮10 |
Outward appearance | Ball, microballoon, bar, ring etc. |
The full scale plant bulk density, kg/m 3 | 500--1100 |
The described catalyst for hydro-upgrading of this patent adds the mixture behind the titanium oxide of 1%--20% (mass percent) with aluminum oxide
Make carrier, metallic sulfide with VIII such as molybdenum, nickel, cobalt, tungsten and VIB is that active metal component and some non-metallic element of family that adds VA family and/or VIIA are auxiliary agent, and the molecular sieve that adds 5%--30% (mass percent) in catalyst for hydro-upgrading is as promotor.Its shape can be sphere, microballoon, bar shaped, go in ring, wheel shape etc.Its manufacturing side adopts saturated spray or saturated pickling process.Its compositing range and physico-chemical property see Table 2.
Table 2 oxygenation modifying catalyst physico-chemical property
Title | Catalyst for coal tar hydrogenation modification |
Chemical constitution, % (quality) | |
?MoO 3 | ?5.0-20.0 |
?WO 3 | ?10-30 |
?NiO | ?1.0-10.0 |
?P | ?0.1-5.0 |
?TiO 2 | ?1%-20% |
Molecular sieve | ?5-30% |
?Al 2O 3 | Surplus |
Physical properties | |
Specific surface, m 2/g | ?70-260 |
Pore volume, ml/g | ?0.20-0.80 |
Crushing strength, N/cm | ?≮15 |
Outward appearance | Ball, microballoon, bar, ring etc. |
The full scale plant bulk density, kg/m 3 | ?500-1100 |
The described coal tar 1 of this patent can be coal tar lighting end less than a certain temperature between 350 ℃ to 500 ℃ as the hydrogenation charging; Full cut that the process coking is processed and/or the coal tar that extracts a certain or certain several chemical substance again; Coal tar without any processing; Extract the coal tar after a certain or certain several chemical substance.The material that extracts is as phenol, naphthalene, etc.After coking processing, not only can improve coking and generate phenol in the oil, the content of naphthalene class material and can reduce iron, nitrogen, the content of solid matter helps hydrogenation processing, can not establish the switch protecting reactor.
The described hydrogenation technique parameter of this patent: the hydrogenator inlet pressure is not more than 15.0Mpa (hydrogen dividing potential drop), initial reaction temperature, 300--390 ℃ (beds medial temperature), volume space velocity 0.4--4.0h
-1, hydrogen-oil ratio 500--3000Nm
3/ m
3
Nomenclature among description of drawings Fig. 1, Fig. 2: 1-coal tar, 2-is less than carbon five lighter hydrocarbons, 3-raw gasline; 4-gas oil; the 5-crude asphalt, 6-high-quality petroleum naphtha, 7-fine-quality diesel oil or fine-quality diesel oil blending component; 8-hydrogenation unconverted oil; the pretreated hydrogenating materials of 9-, 10-preliminary fractionator, 11,12-switch protecting reactor; the 13-hydrogenator, 14-product separation column.
Fig. 3 explanation: 1-coal tar, 2-is less than carbon five lighter hydrocarbons, 3-raw gasline, 4-gas oil, 5-crude asphalt, 6-high-quality petroleum naphtha, 7-fine-quality diesel oil or fine-quality diesel oil blending component, 8-preliminary fractionator, 9-fixed bed hydrogenation reactor, 10-product separation column.
Fig. 4 explanation: 1-coal tar; 2-is less than carbon five lighter hydrocarbons; 3-pulls out a back coal tar, coal tar behind the 4-pre-refining, 5-hydrogenation unconverted oil; 6-high-quality petroleum naphtha; 7-fine-quality diesel oil or fine-quality diesel oil blending component, 8-coal tar flashing tower, 9,10-switch protecting reactor; 11-floating bed hydrogenation reactor, 12-product separation column.
The product of the described hydrogenation technique of embodiment this patent is different with the production purpose and different according to raw material, below with the embodiment explanation.
Embodiment one
Certain vaporization factory by-product coal tar main character sees Table 3.Adopt fixed bed hydrogenation technology and special-purpose catalyst, the catalyzer main character sees Table 4, and the hydrogenation charging is less than 350 ℃ of coal tar lighting ends, and the purpose product is high-quality petroleum naphtha and fine-quality diesel oil blending component.
Go out hydrogenation unit greater than 350 ℃ of cuts as pitch.Do not establish the switch protecting reactor.Its technical process such as Fig. 3.The hydrogenation main technologic parameters sees Table 5.The product main character sees Table 6.
Table 3 coal tar character
The cut scope | Full cut | Less than 350 ℃ of coal tar lighting ends |
Density (20 ℃), g/m 3 | 0.98 | ?0.93 |
Carbon residue, m% | 4.0 | ?2.5 |
Elementary composition, m% | ||
Sulphur | 0.33 | ?0.40 |
Nitrogen | 0.79 | ?0.71 |
Heavy metal, μ g/g | ||
Iron | 33 | ?30 |
Nickel | 0.2 | ?0.18 |
Vanadium | 0.15 | ?0.12 |
Fractional distribution, m% | ||
Less than 200 ℃ | 17 | ?/ |
200--350℃ | 58 | ?/ |
Greater than 350 ℃ | 25 | ?/ |
PONA analysis, m% | ||
| 14 | ?17 |
| 7 | ?8 |
Aromatic hydrocarbons | 54 | ?53 |
Burnt matter | 25 | ?22 |
Table 4 catalyzer main character
Title | Coal tar hydrogenating pre-refining catalyzer | Catalyst for coal tar hydrogenation modification |
Chemical constitution, % (quality) | ||
?MoO 3 | ?5.0-9.0 | ?10.0-11.0 |
?WO 3 | ?/ | ?26.0-30.0 |
?NiO | ?3.0-5.0 | ?2.0-3.0 |
?P | ?1.0-2.0 | ?1.0-2.0 |
?TiO 2 | ?5.0-8.0 | ?8.0-10.0 |
Molecular sieve | ?/ | ?10-15% |
?Al 2O 3 | Surplus | Surplus |
Physical properties | ||
Specific surface, m 2/g | ?100-200 | ?70-100 |
Pore volume, ml/g | ?0.6-0.7 | ?≮0.2 |
Crushing strength, N/cm | ?≮20 | ?≮15 |
Outward appearance | Φ 1.4 * 3-5mm cylinder | Φ 1.4 * 3-5mm cylinder |
The full scale plant bulk density, kg/m 3 | ?0.60-0.70 | ?0.9-1.1 |
Table 5 initial stage main technologic parameters
Catalyzer | Top pre-refining agent, the bottom modifying catalyst |
Volume space velocity, h -1 | 0.7????????????0.85 |
The bed medial temperature, ℃ | ????370 |
The reactor inlet hydrogen-oil ratio, Nm 3/m 3 | ????900 |
Reactor inlet hydrogen dividing potential drop, MPa | ????8.0 |
Chemistry hydrogen consumption, m% | ????2.3 |
Table 6 hydrogenated products main character
Title | Hydrotreated naphtha | Hydrogenated diesel oil |
Density (20 ℃), g/m 3 | ?0.78 | ?0.85 |
Elementary composition, μ g/g | ||
Sulphur | ?15 | ?18 |
Nitrogen | ?8 | ?200 |
The bromine valency, gBr/100g | ?1.0 | ?/ |
Condensation point, ℃ | ?/ | -2 |
Cetane index (ASTM D4737) | ?/ | ?37 |
Boiling range (ASTM D86), ℃ | ||
Initial boiling point | ?70 | ?180 |
10% | ?90 | ?200 |
50% | ?120 | ?240 |
90% | ?150 | ?320 |
Final boiling point | ?190 | ?353 |
Embodiment two
Certain vaporization factory by-product coal tar main character sees Table 3.Adopt ebullated bed technology and special-purpose catalyst, the catalyzer main character sees Table 7, and the hydrogenation charging is full cut coal tar, and the purpose product is high-quality petroleum naphtha and fine-quality diesel oil.Go out hydrogenation unit as needle-shape coke raw material or circulation enters hydrogenator greater than 350 ℃ of unconverted oil cuts.If switch protecting reactor.Its technical process such as Fig. 4.The hydrogenation main technologic parameters sees Table 8.The product main character sees Table 9.
Table 7 catalyzer main character
Title | Coal tar hydrogenating pre-refining catalyzer | Catalyst for coal tar hydrogenation modification |
Chemical constitution, % (quality) | ||
?MoO 3 | ?5.0-9.0 | 10.0-11.0 |
?WO 3 | ?/ | 26.0-30.0 |
?NiO | ?3.0-5.0 | 2.0-3.0 |
?P | ?1.0-2.0 | 1.0-2.0 |
?TiO 2 | ?5.0-8.0 | 8.0-10.0 |
Molecular sieve | ?/ | 15-209% |
?Al 2O 3 | Surplus | Surplus |
Physical properties | ||
Specific surface, m 2/g | ?100-200 | 70-100 |
Pore volume, ml/g | ?0.6-0.7 | ≮0.2 |
Crushing strength, N/cm | ?≮20 | ≮15 |
Outward appearance | Φ 1.4 * 3-5mm cylinder | Microballoon |
The full scale plant bulk density, kg/m 3 | ?0.60-0.70 | 0.9-1.1 |
Table 8 initial stage main technologic parameters
Catalyzer | The pre-refining agent, | Modifying catalyst |
Volume space velocity, h -1 | ????0.7 | ????0.75-1.0 |
The bed medial temperature, ℃ | ????370 | ????375 |
The reactor inlet hydrogen-oil ratio, Nm 3/m 3 | ????900 | ????1000-1200 |
Reactor inlet hydrogen dividing potential drop, MPa | ????8.0 | ????8.0 |
Chemistry hydrogen consumption, m% | ????????????2.3 |
Table 9 hydrogenated products main character
Title | Hydrotreated naphtha | Hydrogenated diesel oil |
Density (20 ℃), g/m 3 | 0.75 | ?0.83 |
Elementary composition, μ g/ | ||
Sulphur | ||
13 | ?17 | |
| 10 | ?180 |
The bromine valency, gBr/100g | 1.0 | ?/ |
Condensation point, ℃ | / | -4 |
Cetane index (ASTM D4737) | / | ?38 |
Boiling range (ASTMD86), ℃ | ||
Initial boiling point | 68 | ?175 |
10% | 90 | ?200 |
50% | 120 | ?240 |
90% | 150 | ?320 |
Final boiling point | 190 | ?355 |
Claims (6)
1. described novel coal tar hydrogenation process of this patent and catalyzer are meant that the coal tar that the coal machining process is produced adopts the novel hydrogenation catalyzer to make with extra care with the method for hydrogenation and/or upgrading production high-quality petroleum naphtha, fine-quality diesel oil or fine-quality diesel oil blending component, the high-quality needle-shape coke raw material, the high-purity chemical product.
2. right 1 described coal tar can be coal tar lighting end less than a certain temperature between 350 ℃ to 500 ℃ as the hydrogenation charging; Full cut that the process coking is processed and/or the coal tar that extracts a certain or certain several chemical substance again; Coal tar without any processing; Extract the coal tar after a certain or certain several chemical substance.The material that extracts is as phenol, naphthalene, quinoline etc.
3. right 1 described new catalyst is meant and utilizes new catalytic material and auxiliary agent to be the special catalyzer of researching and developing of coal tar hydrogenation process.By its role in the described hydrogenation technique of this patent it is divided into two kinds, i.e. hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading.The mixture that hydrogenation pre-refining catalyzer adds with aluminum oxide behind the titanium oxide of 1%--40% (mass percent) is made carrier, is active metal component and adds VA family and/or some non-metallic element of VIIA family is an auxiliary agent with the metallic sulfide of VIII such as molybdenum, nickel, cobalt and VIB.The mixture that catalyst for hydro-upgrading adds with aluminum oxide behind the titanium oxide of 1%--20% (mass percent) is made carrier, be active metal component and add VA family and/or some non-metallic element of VIIA family is an auxiliary agent that with the metallic sulfide of VIII such as molybdenum, nickel, cobalt, tungsten and VIB the molecular sieve that adds 5%--30% (mass percent) in catalyst for hydro-upgrading is as promotor.Being shaped as sphere, microballoon, bar shaped, going in ring of the described catalyzer of this patent, wheel shape, cylinder, trifolium etc.
4. the reactor types of right 1 described hydrogenation technique comprises, fixed bed, ebullated bed, suspension bed and moving-bed.
5. when the hydrogenating materials under the claim 2 is a coal tar without any processing, one to four switch protecting reactor will be set up before the hydrogenator.The described hydrogenation pre-refining of dress this patent catalyzer in the switch protecting reactor, catalyzer adopts the classification filling.
6. right 1 described hydrogenation technique hydrogenator inlet pressure is not more than 15.0Mpa (hydrogen dividing potential drop), initial reaction temperature, 300-390 ℃ (beds medial temperature), volume space velocity 0.4--4.0h
-1, hydrogen-oil ratio 500--3000Nm
3/ m
3
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