CN102008974A - Preparation method and use method of two-stage bed reaction catalyst used in coal tar pitch lightening process - Google Patents
Preparation method and use method of two-stage bed reaction catalyst used in coal tar pitch lightening process Download PDFInfo
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- 239000011294 coal tar pitch Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title abstract description 8
- 239000007809 chemical reaction catalyst Substances 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 32
- 238000005516 engineering process Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 239000011280 coal tar Substances 0.000 claims description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- 239000010426 asphalt Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005336 cracking Methods 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007767 bonding agent Substances 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 230000001404 mediated effect Effects 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000011331 needle coke Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000580063 Ipomopsis rubra Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- -1 cobalt metal oxide Chemical class 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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Abstract
The invention relates to a preparation method and use method of a two-stage bed reaction catalyst used in the coal tar pitch hydrocracking lightening process. The use method of the catalyst comprises the following specific steps: the mixture of coal tar pitch and toluene is used as the raw material and a fixed bed reactor is adopted to perform the efficient combinatorial catalysis through the two-stage bed reaction catalyst under the conditions that the reaction temperature is 380-500 DEG C, the reaction pressure is 5.0-12.0MPa and the reaction air speed is 0.2-5h<-1>, thus realizing the lightening process of the hydrocracking two-stage reaction of coal tar pitch. The two-stage bed combined catalyst in the invention consists of two catalytic components with different functions at a ratio of (1:10)-(10:2). By using the method in the invention in the coal tar pitch hydrocracking lightening reaction process, the reaction activity is higher, the stability is better, the production technology can be effectively simplified, and the production energy consumption, the material consumption and the cost can be reduced.
Description
Technical field
The present invention relates to a kind of preparation method and using method thereof that is used for two sections bed catalysts of coal tar pitch hydrocracking lighting technology.Specifically the mixture with coal tar pitch and toluene is a raw material, adopts fixed bed reactors, by the efficient catalytic effect of these two sections bed combination catalysts, realizes the hydrocracking lighting reaction of coal tar pitch.This method is used for coal tar pitch hydrocracking lighting reaction process, and not only reactivity is higher, lighting yield height, and can effectively simplify production technology, reduces its energy consumption material consumption and cost.
Background technology
China is coal coking big country, and coal tar asphalt accounts for the over half of coal tar total amount.At present, coal tar asphalt is mainly used in production aspects such as modified coal tar pitch buildings waterproof, pitch delay coke, carbon black/needle coke, and what be used to make high value added product utilizes ratio not high, and existing processing and utilization method is easy to produce secondary pollution.On the other hand, constantly soaring and fluctuation along with International Crude Oil, utilize the act as a fuel influence of wet goods factor of coal tar replacement for heavy, cause the rising of domestic coal tar price, and coal tar asphalt is mainly used in some low value-added product scopes, usually the price of this part product is lower than the price of feed coal tar, forms the phenomenon with the cost of material reversal of the natural order of things.Meanwhile, the domestic technique of utilizing coal tar asphalt to produce high-quality pitch coke also is not very ripe, though needle coke has been obtained important breakthrough, the technical international most advanced level that still do not reach, these present situations cause the annual about 6,000,000 tons coal tar pitch resource of China to be difficult to be transformed effectively.
At present, along with petroleum resources face exhaustion, imbalance between supply and demand is growing, and crude oil price skyrockets, and is also sharp risen by the oil product of crude oil production and the price of aromatic hydrocarbon.Simultaneously, produce each fuel oils and chemical products have received great concern by coal tar, each state is all at the process and utilization technology of active development coal tar.CN 20021225737 adopted hydrofinishing or modification technology right＜the lightweight coal tar of 350 ℃ of cuts carries out hydrogenation and produces naphtha and diesel oil.Patent CN 00123146 has proposed the method that a kind of coal tar is produced diesel oil, mainly is for improving the Cetane number of diesel oil, lightweight coal tar is carried out hydrofinishing, reducing the content of aromatic hydrocarbons in the oil product again through dearomatization catalyst.CN 1276059 invented a kind of with low temperature, middle temperature, high temperature coal-tar and from them extraction unit to divide the residue mixed fraction oil behind the chemical industry raw material be raw material, by the combination of hydrofining technology and delay coking process, the method for production chemical product phenol, naphthalene and fuel oil (comprising solvent naphtha, diesel oil or light-weight fuel oil).But the major part that these patents relate to is a lightweight coal tar, and the heavy asphalt in the employing coal tar comes the rare so far report of method of processing aromatic hydrocarbons and each fuel oils as primary raw material.
Japan Patent CN 85105609 disclosed the method for a hydrogenation of coal tar pitch, use the hydrogenation catalyst of refractory inorganic oxide as carrier, this catalyst is the metal of periodic table of elements VI category-B and VIII metalloid element, selects minimum a kind of among hydride, the sulfide.Catalyst contains the VI category-B metal (hydride form) of 6 to 30% weight and the VIII metalloid (oxide form) of at least 1.5% weight, and carrier then mainly is made up of aluminium oxide.This patent is particularly suitable for containing a large amount of insoluble coal tar asphaltes of separating the toluene material, but this patent only is suitable for slight hydrogenation, and degree of hydrogenation still contains the low concentration hetero atom simultaneously, as nitrogen, sulphur, oxygen and metal etc. between 0.03 to 0.5.At present, the hydrocracking technology of coal tar asphalt generally all is the slight hydrogenation to coal tar asphalt, helps the industrial modified coal tar pitch of carbon raw material thereby be translated into, to be applicable to high-quality needle coke and carbon fiber production.But just to the partial hydrogenation of coal tar asphalt raw molecule structure, its complete many cyclic condensations configuration still exists this method of hydrotreating, cracking and molecular weight and molecular weight do not take place and makes coal tar asphalt change the lighting effect of light-end products into.CN 1012503 B have proposed the heavy asphalt of coal tar hydrogenation, the method for coking production needle coke more after treatment.Use supercritical waters such as Han Lina carry out the reaction of lighting to coal tar asphalt, but find to be difficult to control hydrogenation and these two parallel reactions of cracking.
As seen, the coal tar asphalt catalytic hydrogenation of at present domestic and international patent report only is the slight hydrogenation to coal tar asphalt, activity of such catalysts is lower, deep hydrogenation and cracking reaction that perhaps can't the catalytic asphalt component, perhaps be difficult to grasp the balance between hydrogenation and the cracking, change the high added value oil product into thereby cause the molecular weight of coal tar asphalt to be difficult to effectively to reduce lighting.
At present, oneself has 7 kinds through industrialized hydrocracking process approximately in the U.S. both at home and abroad: Isomax, Unicracking/JHC, H-G Hydrocracking, Utracracking, shell adds hydrogenation (Shell) and BASF-IFP hydrocracking, H-GHydrocracking wherein, Utracracking, the shell hydrocracking is mainly used in production gasoline, other several technologies both can be produced gasoline, also can produce aviation kerosine and diesel oil.Difference is little in fact in these several technological processes, and just owing to the different in kind of catalyst, so process conditions, product distributes, and product quality also has nothing in common with each other.Because the technical progress of aspect such as catalyst, the middle pressure hydrocracking technology is developed, is that the purpose conversion ratio is that the middle pressure hydrocracking technology of 40%-70% is succeeded in developing to produce intermediate oil.Mobil, AKZO, Kellogg and Fina four companies unite the technical merit that release MAK-Fining technology has reflected external middle pressure hydrocracking.More the middle pressure hydrocracking technology has been overlapped on the commercial plant on the U.S., Europe and other places and has been used.In recent years, domestic middle pressure hydrocracking technology also has significant progress.Research Institute of Petro-Chemical Engineering (RIPP) and Fushun Petrochemical Research Institute (FRIPP) have developed the middle pressure hydrocracking technology of oneself respectively, wherein the RMC of RIPP (RIPP Middle Pressure Hydrocracking) technology has international most advanced level and uses on commercial plant, and the RMC technology can be represented domestic middle pressure hydrocracking technical merit.
No matter be coal tar pitch processing and utilization method commonly used at present, still comparatively ripe middle pressure hydrocracking technology, and realization coal tar pitch not yet in effect hydrocracking, the coal tar pitch hydrogen addition technology is difficult to reach heavily cracked purpose now, it only is slight hydrogenation, and the existing heavily cracked technology of hydrogenation catalyst, do not used coal tar pitch on the raw material again, coal tar pitch resource huge and the bright prospects used in addition, be necessary to study the coal tar pitch hydrocracking technology of the degree of depth, in the hope of follow-up deep processing is the aromatic hydrocarbons chemical products of various high added values, alleviates the present situation of oil shortage and the clean utilization that is used in coal is arranged.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who is used for two sections bed catalysts of coal tar pitch hydrocracking lighting reaction process, hydrogenation reaction in the coal tar pitch lighting reaction process and these two kinds dissimilar being reflected on two sections bed combination catalysts of cracking reaction are carried out catalytic reaction, thereby two kinds of differential responses are optimized on dissimilar catalyst respectively, but be rendered as a kind of catalyst in the operation, so this method is suitable for all types of fixed bed reactors technologies.
In order to solve above-mentioned the problems of the prior art, the concrete technical scheme that the present invention takes is as follows: a kind of preparation method who is used for two sections bed catalysts of coal tar pitch hydrocracking lighting reaction process, and concrete steps are:
(1) epimere hydrogenation catalysis composition 1 preparation: a inorganic porous material is descended dry 2-10 hour as first kind of carrier at 70-120 ℃, take by weighing slaine, be dissolved in the distilled water, adopt vacuum impregnation technology that carrier is carried out load and modify, tenor is 0.4 ~ 10 wt%; Excessive solution after the vacuum impregnation load is outwelled, take out, be tiled under 70-130 ℃ the environment dry 6-30 hour, be placed in the Muffle furnace 500 ℃ of roastings 3 hours then;
(2) hypomere splitting action catalysis composition 2 preparations: second kind of carrier is by the aluminium oxide bonding agent, polyethylene glycol expanding agent and molecular sieve mixing granulation or extrusion modling, following dry 2 hours after the moulding at 110 ℃, 400～550 ℃ of following roastings after 2 hours, adopt metal-nitrate solutions dipping back molecular sieve 110 ℃ dry 2 hours down, 400～600 ℃ of following roastings 2 hours, finish metal oxide supported modification then, obtain molecular sieve catalytic composition 2;
(3) step (1) hydrogenation catalyst composition 1 and step (2) gained cracking and catalyzing composition 2 weight rates with 1/10 – 10/2 are divided into up and down 2 sections and are loaded in the fixed bed reactors, promptly obtain required two sections bed catalysts.
Among the present invention, inorganic porous material described in the step (1) is selected for use among aluminium oxide, salic silica gel or the MCM-41 a kind of, and through being selected from molybdenum, at least a metal oxide supported modification in nickel or the cobalt, content is 0.4 ~ 20 wt%;
Among the present invention, carrier is selected from SiO described in the step (2)
2/ Al
2O
3Mol ratio is a kind of in Beta, Y, ZSM-5 or the MOR zeolite of 20:1～200:1, adopts 20-50 wt% aluminium oxide as the adhesive moulding, and through chosen from Fe, molybdenum, at least a metal oxide supported modification in nickel or the lanthanum, content is 0.5 ~ 10 wt%.
Two sections bed catalysts that utilize the inventive method to prepare are used for coal tar pitch hydrocracking lighting reaction process, adopt fixed bed reactors, use hydrogen as the reaction carrier gas, carry out the lighting reaction of coal tar asphalt hydrogenation and cracking, 390 ~ 500 ℃ of reaction temperatures, reaction pressure are that 5.0 ~ 12.0MPa, reaction velocity are 0.2 ~ 5 h
-1, the mol ratio of carrier gas and reactant is 3:1 ~ 10:1.
Among the present invention, reactor used internal diameter 20mm, length 600mm, stainless steel; The bead that it is 5mm that reactor bottom is filled one section diameter is as support, and the about 8cm of catalyst that fill at the middle part, the bead that fill on top play the effect of preheating and vaporization raw material; Coal tar asphalt in the raw material and toluene mixture are mixed with hydrogen, and from top to bottom by beds, reaction condition is 390 ~ 500 ℃ of reaction temperatures, be 0.5 ~ 12 h at reaction pressure 1.0 ~ 5.0MPa, reaction velocity
-1, carrier gas/reactant ratio is 3 ~ 10:1(mol/mol).
Raw material uses the mixture of coal tar asphalt and toluene, counts 40-60wt% with mass fraction, and experimental data adopts following formula to calculate.
Technical method of the present invention uses a kind of combined two sections bed catalysis techniques of uniqueness in single reactor, two sections bed catalysts of this uniqueness are easier to realize the dual-use function of hydrogenation and cracking, saved the operation of plant modification or replacement, both can improve activity, the lighting and the isomerization yield of product have been increased again, this invention technology is compared with employed method in the present industrial production, have more flexibility, and have following advantage: technology is simple, operating cost is lower, in same reaction unit, can realize the hydrocracking 2 step reaction of raw material simultaneously, the yield of lightweight aromatic compounds and isoparaffin is considerable, the recyclable utilization of toluene is lost lessly, and can keep good stable.
The specific embodiment
Embodiment 1
1) with SiO
2/ Al
2O
3Mol ratio is that 25 ZSM-5 molecular sieve mixes by aluminium oxide bonding agent and molecular sieve, add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3 wt% is fully mediated evenly, after the moulding 110 ℃ dry 2 hours and 510 ℃ of following roastings after 2 hours down, adopt 7.5wt% nickel nitrate solution dipping back 110 ℃ dry 2 hours down, then 460 ℃ of following roastings 2 hours, promptly finish the burning Ni and modify, obtain the Ni/ZSM-5 of 4.4wt%, be designated as catalyst component 1; 2) dry 14 purpose silica gel 2 hours under 120 ℃ environment, take by weighing the dry good silica-gel carrier of 10g and place a dry mouthful bottle, connect separatory funnel, vavuum pump, the check sealing, vacuumize, adopt 10wt% ammonium molybdate solution dipping back 110 ℃ dry 2 hours down, then 420 ℃ of following roastings 2 hours, promptly finish the load of burning molybdenum and modify, obtain the molybdenum oxide catalyst component 2 of 5.4wt%; 3) catalyst component 1 of above-mentioned two kinds of modified modification difference in functionalitys and catalyst component 2 are closed be designated as the catalyst I.
Embodiment 2
1) with SiO
2/ Al
2O
3Mol ratio is that 60 Y molecular sieve mixes by aluminium oxide bonding agent and molecular sieve, add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3 wt% is fully mediated evenly, after the moulding 110 ℃ dry 2 hours and 530 ℃ of following roastings after 2 hours down, adopt 7.0wt% ammonium molybdate solution dipping back 110 ℃ dry 2 hours down, then 460 ℃ of following roastings 2 hours, promptly finish the load of burning molybdenum and modify, obtain the Mo/Y of catalyst component 1-4.3 wt%; 2) about 2 hours of dry molecular sieves MCM-41 under 100 ℃ environment, adopt 10.0wt% nickel nitrate solution dipping back 110 ℃ dry 2 hours down, 500 ℃ of following roastings 2 hours, promptly finish the burning Ni and modify then, obtain the Ni/MCM-41 of catalyst component 2-7.3wt%; 3) catalyst component 1 of above-mentioned two kinds of modified modification difference in functionalitys and catalyst component 2 are closed be designated as catalyst II.
Embodiment 3
1) with SiO
2/ Al
2O
3Mol ratio is that 23 Beta molecular sieve mixes by aluminium oxide bonding agent and molecular sieve, add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, after the moulding 120 ℃ dry 2 hours and 520 ℃ of following roastings after 2 hours down, adopt 4.0wt% nickel nitrate solution dipping back 110 ℃ dry 2 hours down, then 460 ℃ of following roastings 2 hours, promptly finish the burning Ni and modify, obtain 2.9wt% Ni/Beta.2) dry macroporous aluminium oxide under 120 ℃ environment, adopt 7.0wt% ammonium molybdate solution dipping back 110 ℃ dry 2 hours down, then 500 ℃ of following roastings 2 hours, promptly finish the load of burning molybdenum and modify, obtain 5.9wt% Mo/Al
2O
33) the difference in functionality catalyst component 1 of above-mentioned two kinds of modified modifications and catalyst component 2 are closed be designated as the catalyst III.
Embodiment 4
1) with SiO
2/ Al
2O
3Mol ratio is that 90 MOR molecular sieve mixes by aluminium oxide bonding agent and molecular sieve, add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3 wt% is fully mediated evenly, after the moulding 120 ℃ dry 2 hours and 525 ℃ of following roastings after 2 hours down, adopt 7 wt% cobalt nitrate solutions dipping back following dry 2 hours at 110 ℃, then 440 ℃ of following roastings 2 hours, promptly finish the cobalt metal oxide load and modify, obtain the Co/MOR of 4.1 wt%; Silica white and aluminium oxide bonding agent are mixed, add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3 wt% is fully mediated evenly, after the moulding 100 ℃ dry 2 hours and 510 ℃ of following roastings after 2 hours down, adopt 12 wt% nickel nitrate solutions to flood back 90 ℃ of following dryings 6 hours, then 460 ℃ of following roastings 2 hours, promptly finish the burning Ni and modify, obtain the NiO/ silica gel of 7.8 wt%; 3) catalyst component 1 of above-mentioned two kinds of modified modification difference in functionalitys and catalyst component 2 are closed be designated as the catalyst IV.
Embodiment 5
Adopt fixed bed reactors, use hydrogen, carry out the reaction of coal tar pitch hydrocracking lighting as the reaction carrier gas.Reactor used internal diameter 20mm, length 600mm, stainless steel; The bead that it is 5mm that reactor bottom is filled one section diameter is as support, and the about 8cm of catalyst height that fill at the middle part, the bead that fill on top play the effect of preheating and vaporization raw material; Contain coal tar pitch 45.8% and toluene 54.2 wt% in the raw material, raw material with after hydrogen mixes from top to bottom by beds, reaction condition is that 390 ~ 500 ℃ of reaction temperatures, reaction pressure 5.0 ~ 12MPa, reaction velocity are 0.2 ~ 5 h
-1, carrier gas/reactant H/C ratio is for 1:1 ~ 10:1(mol/mol), concrete catalyst system therefor and response situation see Table 1.To design temperature, feed reaction raw materials with measuring pump behind 500 minutes temperature programming vulcanization reactions, reaction back fluid sample calculates reaction coal tar pitch conversion ratio through the high temperature gas chromatography analysis.
Concrete reaction condition and the catalytic reaction result of implementing of table 1.
Data in the table 1 show, use two sections bed catalysts of the technology of the present invention method all higher with the reactivity that reaction process shows in the hydrocracking lighting of coal tar pitch is processed, light aromatics yield and isomerization yield are higher, and can to continue deep processing be all kinds of high added value aromatic hydrocarbons, its technology is simple, operability height, and the recyclable utilization again of toluene solvant, lower cost makes these two sections bed catalysts have very high potential industrial application value.
Claims (4)
1. preparation method who is used for two sections bed catalysts of coal tar pitch hydrocracking lighting reaction process is characterized in that concrete steps are:
(1) epimere hydrogenation catalysis composition 1 preparation: a inorganic porous material is descended dry 2-10 hour as first kind of carrier at 70-120 ℃, take by weighing slaine, be dissolved in the distilled water, adopt vacuum impregnation technology that carrier is carried out load and modify, tenor is 0.4-10 wt%; Excessive solution after the vacuum impregnation load is outwelled, take out, be tiled under 70-130 ℃ the environment dry 6-30 hour, be placed in the Muffle furnace 500 ℃ of roastings 3 hours then;
(2) hypomere splitting action catalysis composition 2 preparations: second kind of carrier is by the aluminium oxide bonding agent, polyethylene glycol expanding agent and molecular sieve mixing granulation or extrusion modling, following dry 2 hours after the moulding at 110 ℃, 400～550 ℃ of following roastings after 2 hours, adopt metal-nitrate solutions dipping back molecular sieve 110 ℃ dry 2 hours down, 400～600 ℃ of following roastings 2 hours, finish metal oxide supported modification then, obtain molecular sieve catalytic composition 2;
(3) step (1) hydrogenation catalyst composition 1 and step (2) gained cracking and catalyzing composition 2 weight rates with 1/10 – 10/2 are divided into up and down 2 sections and are loaded in the fixed bed reactors, promptly obtain required two sections bed catalysts.
2. a kind of preparation method who is used for two sections bed catalysts of coal tar pitch hydrocracking lighting technology according to claim 1, it is characterized in that inorganic porous material is selected for use among aluminium oxide, salic silica gel or the MCM-41 a kind of described in the step (1), and through being selected from molybdenum, at least a metal oxide supported modification in nickel or the cobalt, content are 0.4-20 wt%.
3. a kind of preparation method who is used for two sections bed catalysts of coal tar pitch hydrocracking lighting technology according to claim 1 is characterized in that carrier is selected from SiO described in the step (2)
2/ Al
2O
3Mol ratio is a kind of in Beta, Y, ZSM-5 or the MOR zeolite of 20:1～200:1, adopts 20-50 wt% aluminium oxide as the adhesive moulding, and through chosen from Fe, molybdenum, at least a metal oxide supported modification in nickel or the lanthanum, content is 0.5-10 wt%.
4. one kind as requiring the preparation method obtains as described in 1 two sections bed catalysts to be used for the using method of coal tar pitch hydrocracking lighting reaction process, it is characterized in that adopting fixed bed reactors, use hydrogen as the reaction carrier gas, carry out the lighting reaction of coal tar asphalt hydrogenation and cracking, reaction temperature 390-500 ℃, reaction pressure is that 5.0-12.0MPa, reaction velocity are 0.2-5 h
-1, the mol ratio of carrier gas and reactant is 3:1-10:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102212391A (en) * | 2011-05-11 | 2011-10-12 | 同济大学 | Process method for preparing oil by hydrocracking and upgrading coal tar pitch |
| CN102212393A (en) * | 2011-05-11 | 2011-10-12 | 同济大学 | Method for preparing oil through lightening in coal tar pitch hydrogenation and cracking second-order reaction |
| CN104788974A (en) * | 2015-04-20 | 2015-07-22 | 太原科技大学 | Road asphalt modifier and preparation method thereof |
| CN109415279A (en) * | 2016-06-14 | 2019-03-01 | 氟石科技公司 | Gasification tar is processed into BTX with high yield |
| CN111234860A (en) * | 2020-02-21 | 2020-06-05 | 陕西华大骄阳能源环保发展集团有限公司 | Method for upgrading and lightening asphaltene |
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| CN102212393A (en) * | 2011-05-11 | 2011-10-12 | 同济大学 | Method for preparing oil through lightening in coal tar pitch hydrogenation and cracking second-order reaction |
| CN104788974A (en) * | 2015-04-20 | 2015-07-22 | 太原科技大学 | Road asphalt modifier and preparation method thereof |
| CN109415279A (en) * | 2016-06-14 | 2019-03-01 | 氟石科技公司 | Gasification tar is processed into BTX with high yield |
| CN111234860A (en) * | 2020-02-21 | 2020-06-05 | 陕西华大骄阳能源环保发展集团有限公司 | Method for upgrading and lightening asphaltene |
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