CN101927167A - Compound coal tar hydrogenation catalyst and preparation method thereof - Google Patents
Compound coal tar hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN101927167A CN101927167A CN 201010217361 CN201010217361A CN101927167A CN 101927167 A CN101927167 A CN 101927167A CN 201010217361 CN201010217361 CN 201010217361 CN 201010217361 A CN201010217361 A CN 201010217361A CN 101927167 A CN101927167 A CN 101927167A
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Abstract
The invention relates to a compound coal tar hydrogenation catalyst and a preparation method thereof. The catalyst comprises a high-activity component of water-soluble salts of molybdenum, nickel, cobalt or tungsten and comprises a low-activity component of iron oxide ore or iron sulfide ore, wherein the mass ratio of the metals in the high-activity component to the metals in the low-activity component is 1:1,000 to 1:10; iron accounts for more than or equal to 40 weight percent of the ore; and water accounts for less than 2 weight percent of the catalyst. The catalyst is used for the coal tar hydrocracking technical process in a suspension bed, has higher hydrogenation activity and the lightweight oil yield of over 94 percent, and can be recycled; the preparation and use cost of the catalyst can be greatly reduced, the consumption of the catalyst is reduced in the process, the coke deposition of the reaction system is avoided simultaneously and the operation cycle is prolonged.
Description
Technical field
The present invention relates to a kind of coal tar hydrogenating process catalyst, relating in particular to a kind of is raw material with coal tar, by hydrogenation and cracking reaction, is used to a kind of compound coal tar hydrogenation catalyst of producing engine fuel and/or industrial chemicals and preparation method thereof.
Background technology
Coal tar is important byproduct in the pyrolysis of coal distillation process process, it is the complex mixture of multiple material, different according to pyrolysis of coal pyrolysis temperature and process approach, coal tar can be divided into coalite tar, medium temperature coal tar and high temperature coal-tar, and it is bigger that it forms difference.
At present, the process of China's coal tar routine is to distill the various cuts that cut in the diversity through preliminary treatment, adopt physics or chemical method (as acid-alkali washing, distillation, polymerization, method for crystallising) to handle to various cuts again and extract various chemical products, also have greatly and directly burnt as thick fuel replacement for heavy.Traditional processing method technology is more backward, separation and purification difficulty are bigger, be difficult for the formation scale, can produce large amount of sewage, waste residue simultaneously, contaminated environment, in addition, owing to coal tar sulphur, nitrogen compound content height, directly burning can produce a large amount of SOx and NOx class material, causes serious environmental to pollute.Therefore, the cleaning of coal tar processing and effective utilization also become all the more important.
Utilize hydrogenation technique can effectively remove impurity such as sulphur nitrogen in the coal tar, reduce its density, realize lighting.Compare with the oil heavy distillate, coal tar raw material has content of heteroatoms height, ash content height, characteristics such as polycyclic aromatic hydrocarbon content height, colloid, asphalt content height.This makes coal tar have the quick coking and deactivation of catalyst, the problem that the life-span is short when adopting conventional oil hydrogenation catalyst and technical process.
In the PETROLEUM PROCESSING field, many heavy oil floating bed hydrogenation catalyst have been developed, Chinese patent CN1132910C, CN1133727C, CN1107712C disclose oil-soluble suspension bed hydrogenation catalyst, though this class catalyst has good dispersiveness, exist weak points such as cost of material height, Preparation of Catalyst cost height.
Chinese patent CN1952064A, CN1233798C, CN1243082C, CN1050151C, CN1133725C, CN1482214A, US4637871, US5039392 etc. have proposed the using method of water-soluble disperse type catalyzer, the advantage of these class methods is good dispersions of catalyst activity component, its weak point is in use to need the large quantity of moisture that catalyst is brought into is removed, and has increased dehydration and expense.
Chinese patent CN1234816C discloses a kind of suspension bed residual oil hydrogenation catalyst with catalysis, coke trapping function, wherein the catalyst activity component is I B family and/or VIII family element or its mixture in the periodic table of elements, carry burnt body and can select coal dust, graphite powder or activated carbon powder etc. for use, be used for carrying the coke that the course of reaction polymerisation generates.With the water soluble salt of I B family and/or VIII family element or its mixture with carry a burnt body and mix in proportion, dewater and promptly make multifunctional suspending bed residual oil hydrocatalyst, the characteristics of this multifunction catalyst are that catalytic active component is stated from the carbon-containing carrier of inertia, and catalyst is difficult to repeatedly regeneration and reuses.
Contain hetero atoms such as a large amount of sulphur, nitrogen, oxygen and polycyclic aromatic hydrocarbon, colloid, asphalitine in the coal tar, its cracking performance is poor, and polycondensation generates active component inactivation, the reaction system coking that big molecule coke makes conventional hydrogenation catalyst easily under the high-temperature hydrogenation reaction condition, therefore, come the engine fuel of production lightweight and/or industrial chemicals problems such as reaction system coking deposition, catalyst weak point in service life will occur with conventional hydrogen addition technology reconstructed coal tar.
Summary of the invention
The objective of the invention is to overcome above-mentioned prior art and have deficiency and problem, exploitation provides a kind of and is repeatedly used, and increases substantially the result of use of catalyst, compound coal tar hydrogenation catalyst of the cost of reduction catalyst and preparation method thereof.
Compound coal tar hydrogenation catalyst provided by the invention comprises high-activity component and low activity component, and wherein the weight ratio of high-activity component metal and low activity component metals is 1: 1000 to 1: 10, is preferably 1: 1000 to 1: 100; A kind of or the polymetallic water soluble salt compounds that described high activity metal component is metals such as molybdenum, nickel, tungsten or cobalt a kind of or the mixture that mixes with any ratio, for example sulfate or nitrate or ammonium salt etc.; Described low activity metal component is for example bloodstone or an iron sulfide ore of ferric oxide ore, and wherein iron in ore content preferably is not less than 40wt%, and the compound coal tar hydrogenation catalyst granularity is the powdered granule of 1-100 μ m, and its water content is lower than 2wt%.
The preparation method of compound coal tar hydrogenation catalyst provided by the invention, it is characterized in that low activity component ferric oxide ore or pyrites stone flour are broken into the powdered granule of 1～100 μ m, in crushing process, the water soluble salt of metals such as molybdenum, nickel, tungsten or cobalt for example the aqueous solution of a kind of or its mixture of sulfate or nitrate or ammonium salt (can appoint ratio to mix) spray the ore particles surface, the weight ratio of spray flux control high-activity component metal and iron is 1: 1000 to 1: 10, is preferably 1: 1000 to 1: 100; The crushing process temperature is a room temperature to 120 ℃, is preferably 80 to 120 ℃, makes the water evaporates of the aqueous solution that sprays the ore particles surface, obtains the compound coal tar hydrogenation catalyst powdered granule that water content is lower than 2wt%.
The using method of compound coal tar provided by the invention (suspension bed) hydrogenation catalyst is: catalyst powder that (1) usefulness obtains and recycle oil or coal tar raw material oil are mixed into the uniform catalyst slurry oil, the concentration of oil-catalyst slurry can be controlled in 20～45wt%, preferably is controlled at 25～40wt%.Promptly made compound coal tar suspension bed hydrogenation catalyst slurry oil, (2) oil-catalyst slurry and coal tar raw material are mixed into suspended-bed reactor, before the coal tar raw material increasing temperature and pressure, oil-catalyst slurry and coal tar raw material are mixed, mixed proportion is: the amount of metal of active component (total metal content) is 0.1: 100 to 4: 100 with the ratio of coal tar raw material weight, is preferably 0.5: 100 to 2: 100.Add for example dimethyl sulfide etc. of vulcanizing agent simultaneously, the addition of vulcanizing agent should guarantee that hydrogen sulfide content is not less than 1000ppm in the systemic circulation hydrogen.(3) behind frequent pressure fractionating tower of reaction product or the atmospheric flash tower, before about 2/3rds to 4/5ths heavy oil of the normal end is recycled directly to reactor as recycle oil, be mixed into reactor with feedstock oil, heavy oil of the remaining normal end enters the catalyst regeneration retracting device.(4) catalyst recovery process: the heavy oil of the normal end that will contain solid catalyst mixes with an amount of naphtha, after sedimentation, filtration, obtain taking off solid oil and used solid catalyst, wherein take off solid oil and return to product fractionating column separation naphtha, used solid catalyst can be hybridly prepared into oil-catalyst slurry with fresh catalyst and recycle once more after 500～700 ℃ of roastings, removing its surperficial coke.
Compound (suspension bed) provided by the invention coal tar hydrogenation catalyst and preparation method thereof characteristics are, (1) adopt high-activity component and low activity hydrogenation component compound in proportion, obtain being suitable for the catalyst activity of coal tar hydrogenating, when realizing that coal tar transforms, can reduce Preparation of catalysts and use cost to greatest extent, compare with the catalyst of single high-activity component, composite catalyst of the present invention can reduce the Preparation of Catalyst cost.(2) catalyst repeatedly regeneration cycle use, reduced the use amount of catalyst in the coal tar hydrogenating process.(3) adopt grained catalyst to be suspended in the coal tar, can carry a small amount of big molecule coke that polycondensation generates in the course of reaction, avoid these coke laydowns to influence the normal operation of equipment, the on-stream time of extension fixture at reaction system.
The specific embodiment
The present invention further specifies the present invention with the following example, but protection scope of the present invention is not limited to the following example.
Embodiment 1: catalyst and preparation thereof
With iron content is that (Main Ingredients and Appearance is Fe to the 58wt% bloodstone
2O
3) be ground into powdered granule less than 100 μ m, then 10% ammonium molybdate aqueous solution is sprayed equably on particle, spray flux is approximately molybdenum: the iron weight ratio equals 1: 500, dried 1 hour down through 100 ℃, obtain the powdered granule catalyst of water content less than 0.5wt%, its granularity is less than 100 μ m.
Embodiment 2: catalyst and preparation thereof
Embodiment 2 is identical with example 1 preparation technology, and not being both iron ore is troilite.
Embodiment 3: the coal tar hydrogenating test
Present embodiment is handled the test of coal tar for adopting suspension bed hydrogenation process, and concrete operations are as follows: present embodiment selects for use a kind of typical coal tar as test raw material, and the character of the pretreated coal tar raw material of process sees the following form:
Light oil second pyrolysis in coal tar raw material produces more gas, in the present embodiment, the full raw material of coal tar is carried out separated, isolate naphtha cut and diesel oil distillate, only coal tar is carried out hydrocracking lighting reaction greater than 370 ℃ of cuts as the raw material of floating bed hydrogenation reactor, the light oil fraction that the full cut separated of light oil fraction that product is separated and coal tar is come out is carried out upgrading processing fuel oil and industrial chemicals together again.
The catalyst that makes for embodiment 1 of test catalyst system therefor makes oil-catalyst slurry with catalyst greater than the part of 370 ℃ of heavy distillates with coal tar under 80 ℃ stirring condition, the solid concentration of controlling catalyst slurry is about 25wt%.The test catalyst system therefor is the powdery molybdenum-iron composite catalyst of granularity less than 100 μ m, and molybdenum: iron equals 1: 500 (weight ratio), and vulcanizing agent is a dimethyl disulfide.The direct recycle oil that contains catalyst (about 4/5ths heavy oil of the normal end) behind oil-catalyst slurry and vulcanizing agent, all the other most of coal tar heavy fractioning raw materials and the frequent pressure fractionating tower of floating bed hydrogenation reaction product (or atmospheric flash tower) is mixed then, enters the floating bed hydrogenation reactor and carry out hydrocracking reaction after feedstock pump boosts, mixes the hydrogen intensification.The addition of catalyst is 0.8: 100 with the ratio of amount of metal and the coal tar raw material weight of control active component, obtains liquid-solid phase from the suspended-bed reactor effluent after through high-temperature separator, cold catch pot and just divides oil mixture stream and hydrogen-rich gas two parts.Hydrogen-rich gas is as recycle hydrogen.After liquid-solid phase is just divided the frequent pressure fractionating tower of oily logistics, cat head obtains less than 370 ℃ of light distillates, the heavy oil major part of the normal end (about 4/5ths) that contains catalyst is recycled directly to as recycle oil further carries out hydrogenation lighting reaction in the floating bed hydrogenation reactor, the heavy oil of the normal end of fraction (about 1/5th) that will contain solid catalyst mixes with an amount of naphtha, through sedimentation, obtain taking off solid oil and used solid catalyst after the filtration, wherein taking off solid oil returns to after the product fractionating column separates naphtha, be circulated to the further hydrogenation lighting of floating bed hydrogenation reactor together with heavy oil of the normal end, used solid catalyst is through 500～700 ℃ of roastings, remove (seeing embodiment 4 for details) behind its surperficial coke, can be hybridly prepared into oil-catalyst slurry with fresh catalyst and recycle once more.
Test scale be 1 kg of oil/hour continuous suspension bed experimental rig on carry out process conditions such as following table:
| Reaction temperature, ℃ | 450 |
| The reactive hydrogen dividing potential drop, MPa | 17 |
| Air speed, h -1 | 1.0 |
| Hydrogen-oil ratio, v/v | 800 |
| Catalyst (comprising regenerative agent) addition (iron+molybdenum)/oil | 0.8/100 |
| The normal direct internal circulating load of end heavy oil/go vacuum tower to take off solid amount | 4/1 |
| Vulcanizing agent/feedstock oil | 2/100 |
Gained portion of product yield distribution result such as following table under these conditions:
| Product: | |
| Naphtha yield, wt% | 11.9 |
| Diesel yield, wt% | 39.3 |
| Heavy-oil hydrogenation transforms＜370 ℃ of light oil productive rates: | |
| Gasoline yield, wt% | 13.4 |
| Diesel yield, wt% | 29.5 |
| The light oil productive rate amounts to, wt% | 94.1 |
As seen, adopt coal tar hydrogenation catalyst of the present invention, can make the light oil productive rate reach 94.1%.
Embodiment 4: catalyst regeneration
With 1/4th of the atmospheric residue that contains catalyst that obtains among the embodiment 3, naphtha with 1.5 times of weight dilutes, filter out solid particle (catalyst that mainly was to use) then, with solid particle 120 ℃ of oven dry 1 hour in vacuum drying oven successively, 600 ℃ of roastings 1.5 hours in horse still stove, the catalyst after will regenerating at last mixes use with fresh catalyst according to 1: 9 ratio again.
Claims (4)
1. compound coal tar hydrogenation catalyst, it is characterized in that comprising high-activity component and low activity component, wherein the weight ratio of high-activity component metal and low activity component metals is 1: 1000 to 1: 10, and described high-activity component is water soluble salt compounds or its mixture of molybdenum, nickel, cobalt or tungsten metal; The low activity component is ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, and the catalyst water content is lower than 2wt%, and particle diameter is the powdered granule of 1～100 μ m.
2. according to the compound coal tar hydrogenation catalyst of claim 1, the weight ratio that it is characterized in that described high-activity component metal and low activity component metals is 1: 1000 to 1: 100, and described water soluble salt compounds is sulfate or nitrate or ammonium salt.
3. the preparation method of claim 1 or 2 compound coal tar hydrogenation catalyst, it is characterized in that low activity component ferric oxide ore or pyrites stone flour are broken into the powdered granule of 1～100 μ m, in crushing process molybdenum, nickel, a kind of water soluble salt of cobalt or tungsten metal or the aqueous solution of its mixture spray the ore particles surface, the weight ratio of spray flux control high-activity component metal and low activity component metals is 1: 1000 to 1: 10, the crushing process temperature is a room temperature to 120 ℃, makes the water evaporates of the aqueous solution that sprays the ore particles surface obtain the compound coal tar hydrogenation catalyst that water content is lower than 2wt%.
4. according to the preparation method of claim 3 compound coal tar hydrogenation catalyst, the weight ratio that it is characterized in that high-activity component metal and low activity component metals is 1: 1000 to 1: 100, and described crushing process temperature is 80～120 ℃.
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