CN1115387C - Process for deeply desulfurizing fractional oil with low hydrogen consumption - Google Patents
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- CN1115387C CN1115387C CN 00132562 CN00132562A CN1115387C CN 1115387 C CN1115387 C CN 1115387C CN 00132562 CN00132562 CN 00132562 CN 00132562 A CN00132562 A CN 00132562A CN 1115387 C CN1115387 C CN 1115387C
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Abstract
The present invention discloses a deep desulfurizing method with low hydrogen consumption for distillate oil. Raw materials of diesel oil and hydrogen gas contact a hydrofining catalyst under the conditions of 2.0 to 8.0MPa of hydrogen partial pressure, 320 to 440 DEG C of temperature, 2 to 7h<-1> of liquid hourly space velocity and 200 to 700Nm<3>/m<3> of a total hydrogen oil ratio. A reaction effluent is not separated and contact the hydrofining catalyst under the conditions of 200 to 290 DEG C of temperature and 4 to 10h<-1> of liquid hourly space velocity. The reaction effluent is separated, wherein a liquid product enters a fractionating system, and hydrogen gas enriching hydrogen circulates back to the reactor. The chemical hydrogen consumption of the present invention is low, and the sulfur content of a diesel oil product can be lowered to lower than 300 ppm.
Description
The invention belongs to a kind of is the method that obtains the refining hydrocarbon ils of low boiler cut existing under the situation of hydrogen, more particularly, is a kind of process for deeply desulfurizing fractional oil of low hydrogen consumption.
Along with the reinforcement of environmental consciousness, for reducing vehicle exhaust to atmospheric pollution, people are to the increasingly stringent that requires of foreign matter content such as sulphur, nitrogen in the diesel oil distillate.Just carried out the sulfur specifications diesel oil index that sulphur content is up to 500ppm in 1997 as Europe, in 2000 diesel oil sulphur content index dropped to and be not more than 350ppm, will drop to again to sulphur content specification in 2005 and be not more than 50ppm.California, USA resource management office (CARB) and U.S. environment management association (EMA) have also proposed the low-sulfur diesel-oil index of oneself.At home, China Petrochemical Corp. has also revised new diesel product specification, and the specification requirement sulphur content is less than 0.20m%.Metropolitan diesel oil specification also resembles the content of impurity such as further restriction sulphur Europe, the U.S., nitrogen, and the sulphur content that requires diesel product is less than 500ppm.For this reason, each oil refining enterprise all will face the problem of improving the catalytic diesel oil quality.
Adopt conventional hydrofinishing process or highly active Hydrobon catalyst, though also can reach the purpose of desulfurization, along with the intensification of the hydrogenation degree of depth, the aromatic hydrocarbons saturation capacity increases, and chemical hydrogen consumption increases.The load that this certainly will will increase new hydrogen or circulating hydrogen compressor also may need to change compressor in case of necessity.In addition, concerning the little refinery of some hydrogen source, the unit hydrogen consumption of hydrogenation unit increases and means that the treatment capacity of device will reduce.So a main difficult point of research is the problem that how to solve chemical hydrogen consumption when reducing the hydrogenated products sulphur content at present, just how to control the generation of taking off the aromatic hydrocarbons reaction, hydrogenating desulfurization selectively.
Prior art mostly is to adopt two reactors, removes the sulphur that more easily removes at first reactor, tries every possible means to increase the operating severity of second reactor then, removes the sulphur content that difficulty is taken off part, reaches the purpose of deep desulfuration.
Wherein a kind of method is to increase separation system, promptly increases a high-pressure separator between two reactors, removes the hydrogen sulfide in first reactor product, and the new hydrogen purity that enters second reactor is improved, and reaches the purpose of deep desulfuration with this.
The method of another kind of deep desulfuration is the flow direction that changes logistics.This method generally adopts hydrogenating materials to enter from the reactor middle part, and new hydrogen enters from reactor bottom; At reactor top hydrogen and hydrogenating materials and stream process beds, reverse through beds at reactor lower part raw material and hydrogen.On the lower reactor top of hydrogen dividing potential drop, remove the sulphur in the light constituent; And, remove the sulfur impurity in the heavy constituent at the higher reactor lower part of hydrogen dividing potential drop.At last light, heavy constituent are mixed, reach the purpose of deep desulfuration.
For example, at USP5, introduced a kind of method of two-stage hydrogenation desulfurization in 114,562.At least adopt two reaction zones in this method, load non-precious metal catalyst in first reaction zone, second general noble metal catalyst that loads the metal sulfur sensitive of reaction zone, the hydrogen dividing potential drop is than the high 500kPa of first reaction zone, and temperature of reaction is lower than first reaction zone.A high temperature stripper plant is arranged, to remove the hydrogen sulfide in first reaction zone product between two reactors.Though this method can obtain the diesel product of low-sulfur, low aromatic hydrocarbons, because aromatic hydrocarbons saturated in a large number in the raw material causes chemical hydrogen consumption to increase.
The objective of the invention is to provide on the basis of existing technology a kind of process for deeply desulfurizing fractional oil of low hydrogen consumption, be lower than the diesel product of 350ppm with the production sulphur content.
Method provided by the invention is: diesel raw material contacts with Hydrobon catalyst in first bed with hydrogen, and reaction conditions is: the best 3.0～6.5MPa of hydrogen dividing potential drop 2.0～8.0MPa, 320～440 ℃ best 350～400 ℃ of temperature, liquid hourly space velocity (hereinafter to be referred as LHSV) 2～7h
-1Best 3～5h
-1, total hydrogen-oil ratio 200～700Nm
3/ m
3Best 300～600Nm
3/ m
3, the effluent of first bed enters second bed without separation, contacts with hydrogen, Hydrobon catalyst, and reaction conditions is: the best 3.0～6.5MPa of hydrogen dividing potential drop 2.0～8.0MPa, 200～290 ℃ best 240～280 ℃ of temperature, LHSV 4～10h
-1Best 6～8h
-1, reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and gas is through purifying, and rich hydrogenous gas circulation is returned reactor.
Described diesel raw material is straight-run diesel oil, catalytic cracking diesel oil, coker gas oil or its mixture.The boiling range scope of diesel raw material is 140～390 ℃ and is preferably 180～370 ℃ that sulphur content is 0.1～3.0 heavy %.
First bed and the series connection of second bed can be in same fixed-bed reactor, also can be in two different fixed-bed reactor.The severe reaction conditions of first bed shows as the temperature height, air speed is low, and in this bed, the sulphur in the diesel raw material is by hydrogenation and removing significantly, and aromaticity content is constant substantially; And the reaction conditions of second bed relaxes relatively, shows as that temperature is low, air speed is high, in this reactor, to improve the color of diesel oil distillate.The temperature of reaction of two beds can adopt cold hydrogen or cold oil to circulate and control.
The used Hydrobon catalyst of first bed and second bed is identical, this catalyzer can be VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, preferably consisting of of Hydrobon catalyst: 1～5 heavy % nickel oxide, 12～35 heavy % Tungsten oxide 99.999s, 1～9 heavy % fluorine and surplus aluminum oxide.When carbon residue in the diesel raw material or metal content are higher; for preventing that the beds coking from causing bed pressure drop too fast; can add a certain amount of hydrogenation protecting agent at the Hydrobon catalyst top of first bed; with the running of assurance device long period ground, the add-on of hydrogenation protecting agent is generally 1～20 volume % of Hydrobon catalyst.This hydrogenation protecting agent is made up of the gamma-aluminium oxide carrier with diplopore distribution of 1.0～5.0 heavy % nickel oxide, 5.5～10.0 heavy % molybdenum oxides and surplus.
The invention has the advantages that:
1, this method is the single hop flow process, and only uses a kind of Hydrobon catalyst, and technical process is simple, is convenient to operation, utilizes existing apparatus to carry out appropriate reconstruction and can implement;
2, the sulphur content of diesel product is below 150ppm, and the sulphur content of product is lower than 50ppm when especially being raw material with straight-run diesel oil.The chemical hydrogen consumption of this method substantially all is used for desulphurization reaction, and aromaticity content changes very little, and reaching the chemical hydrogen consumption of installing behind the deep desulfuration increases seldom, and compared with prior art, chemical hydrogen consumption can reduce more than 40%;
3, the refining section in cryogenic back can be improved the character such as color of product, makes other index of diesel product reach specification requirement;
4, this method has bigger flexibility of operation, can adjust operating parameters according to product requirement.Produce the product of different sulphur content specifications;
5, working pressure is relatively low.Because this method is operated under middle pressure, thereby has reduced plant investment, has reduced process cost; Because this method is operated under middle pressure, thereby has reduced plant investment, has reduced process cost.
Following example will give further instruction to present method, but therefore not limit present method.
Diesel raw material character among the embodiment is as shown in table 1.The trade names of employed Hydrobon catalyst, hydrogenation protecting agent are respectively RN-10, RG-1 among the embodiment, produce by Sinopec Group's Chang Ling oil-refining chemical head factory catalyst plant, and its composition and physico-chemical property are as shown in table 2.
Embodiment 1
Straight-run diesel oil A raw material and hydrogen enter first bed, at hydrogen dividing potential drop 3.2MPa, 370 ℃ of temperature, LHSV3.0h
-1, hydrogen-oil ratio 200Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 3.2MPa, 240 ℃ of temperature, LHSV6.0h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 3, and as can be seen from Table 3, the sulphur content of diesel oil distillate is 128ppm in the product, and desulfurization degree is 98.7%, and chemical hydrogen consumption is 0.58%.
Embodiment 2
Straight-run diesel oil A raw material and hydrogen enter first bed, at hydrogen dividing potential drop 3.2MPa, 380 ℃ of temperature, LHSV3.0h
-1, hydrogen-oil ratio 200Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 3.2MPa, 240 ℃ of temperature, LHSV6.0h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 3, and as can be seen from Table 3, the sulphur content of diesel oil distillate is 87ppm in the product, and desulfurization degree is 99.1%, and chemical hydrogen consumption is 0.56%.
Embodiment 3
Straight-run diesel oil A raw material and hydrogen enter first bed, at hydrogen dividing potential drop 3.2MPa, 390 ℃ of temperature, LHSV3.0h
-1, hydrogen-oil ratio 200Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 3.2MPa, 240 ℃ of temperature, LHSV6.0h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 3, and as can be seen from Table 3, the sulphur content of diesel oil distillate is 56ppm in the product, and desulfurization degree is 99.4%, and chemical hydrogen consumption is 0.50%.
Embodiment 4
Straight-run diesel oil A raw material and hydrogen enter first bed, at hydrogen dividing potential drop 3.2MPa, 390 ℃ of temperature, LHSV4.0h
-1, hydrogen-oil ratio 200Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 3.2MPa, 240 ℃ of temperature, LHSV8.0h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 3, and as can be seen from Table 3, the sulphur content of diesel oil distillate is 114ppm in the product, and desulfurization degree is 98.9%, and chemical hydrogen consumption is 0.51%.
Embodiment 5
Catalytic cracking diesel oil raw material and hydrogen enter first bed, at hydrogen dividing potential drop 6.4MPa, 370 ℃ of temperature, LHSV2.4h
-1, hydrogen-oil ratio 600Nm
3/ m
3Condition under contact with hydrogenation protecting agent RG-1, Hydrobon catalyst RN-10 (RG-1 is the 10 volume % of RN-10) successively, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 6.4MPa, 260 ℃ of temperature, LHSV5.6h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 4, and as can be seen from Table 4, the sulphur content of diesel oil distillate is 91ppm in the product, and desulfurization degree is 98.4%, and chemical hydrogen consumption is 0.90%.
Embodiment 6
Catalytic cracking diesel oil raw material and hydrogen enter first bed, at hydrogen dividing potential drop 6.4MPa, 370 ℃ of temperature, LHSV2.6h
-1, hydrogen-oil ratio 500Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 6.4MPa, 280 ℃ of temperature, LHSV6.0h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 4, and as can be seen from Table 4, the sulphur content of diesel oil distillate is 115ppm in the product, and desulfurization degree is 97.9%, and chemical hydrogen consumption is 0.89%.
Embodiment 7
Catalytic cracking diesel oil raw material and hydrogen enter first bed, at hydrogen dividing potential drop 6.4MPa, 370 ℃ of temperature, LHSV2.9h
-1, hydrogen-oil ratio 500Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 6.4MPa, 280 ℃ of temperature, LHSV6.7h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 4, and as can be seen from Table 4, the sulphur content of diesel oil distillate is 150ppm in the product, and desulfurization degree is 97.3%, and chemical hydrogen consumption is 0.86%.
Embodiment 8
Catalytic cracking diesel oil raw material and hydrogen enter first bed, at hydrogen dividing potential drop 6.4MPa, 370 ℃ of temperature, LHSV2.1h
-1, hydrogen-oil ratio 500Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 6.4MPa, 280 ℃ of temperature, LHSV5.0h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 4, and as can be seen from Table 4, the sulphur content of diesel oil distillate is 95ppm in the product, and desulfurization degree is 98.3%, and chemical hydrogen consumption is 0.96%.
Embodiment 9
Straight-run diesel oil B raw material and hydrogen enter first bed, at hydrogen dividing potential drop 3.2MPa, 370 ℃ of temperature, LHSV3.0h
-1, hydrogen-oil ratio 300Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 3.2MPa, 280 ℃ of temperature, LHSV4.5h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 5, and as can be seen from Table 5, the sulphur content of diesel oil distillate is 36ppm in the product, and desulfurization degree is 99.7%, and chemical hydrogen consumption is 0.60%.
Embodiment 10
Straight-run diesel oil B raw material and hydrogen enter first bed, at hydrogen dividing potential drop 3.2MPa, 380 ℃ of temperature, LHSV3.0h
-1, hydrogen-oil ratio 300Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 3.2MPa, 280 ℃ of temperature, LHSV4.5h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 5, and as can be seen from Table 5, the sulphur content of diesel oil distillate is 22ppm in the product, and desulfurization degree is 99.8%, and chemical hydrogen consumption is 0.56%.
Embodiment 11
Straight-run diesel oil B raw material and hydrogen enter first bed, at hydrogen dividing potential drop 6.4MPa, 360 ℃ of temperature, LHSV2.6h
-1, hydrogen-oil ratio 500Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 6.4MPa, 280 ℃ of temperature, LHSV6.0h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 5, and as can be seen from Table 5, the sulphur content of diesel oil distillate is 21ppm in the product, and desulfurization degree is 99.8%, and chemical hydrogen consumption is 0.71%.
Embodiment 12
Straight-run diesel oil B raw material and hydrogen enter first bed, at hydrogen dividing potential drop 6.4MPa, 370 ℃ of temperature, LHSV2.9h
-1, hydrogen-oil ratio 500Nm
3/ m
3Condition under contact with Hydrobon catalyst RN-10, the effluent of first bed enters second bed without separation, at hydrogen dividing potential drop 6.4MPa, 280 ℃ of temperature, LHSV6.7h
-1Condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two beds.
The character of processing condition and main products is as shown in table 5, and as can be seen from Table 5, the sulphur content of diesel oil distillate is 22ppm in the product, and desulfurization degree is 99.8%, and chemical hydrogen consumption is 0.80%.
Table 1
| Diesel raw material | Straight-run diesel oil A | Catalytic cracking diesel oil | Straight-run diesel oil B |
| Density, g/cm 3 | 0.8364 | 0.9080 | 0.8424 |
| S，ppm | 10100 | 5509 | 12500 |
| N，ppm | 66 | 632 | 68 |
| Total aromatic hydrocarbons, m% | 30.3 | 50.7 | 20.2 |
| Mononuclear aromatics | 17.8 | 17.3 | 12.5 |
| The above aromatic hydrocarbons of dicyclo | 12.5 | 33.4 | 6.7 |
| Colourity | 0.5 | ＜5.0 | ＜1.0 |
| Boiling range (ASTMD86), ℃ | |||
| Initial boiling point | 205 | 214 | 228 |
| 10％ | 241 | 245 | 259 |
| 30％ | 261 | 270 | 276 |
| 50％ | 272 | 295 | 286 |
| 70％ | 301 | 323 | 309 |
| 90％ | 350 | 352 | 344 |
| Do | 390 | 373 | 371 |
Table 2
| Catalyst type | Hydrofining | Protective material |
| The catalyzer trade mark | RN-10 | RG-1 |
| Nickel oxide, heavy % | 4.0 | 1.2 |
| Tungsten oxide 99.999, heavy % | 26.0 | (5.5 molybdenum oxide) |
| Fluorine, heavy % | 2.0 | - |
| Specific surface, rice 2/ gram | 230 | 205 |
| Pore volume, milliliter/gram | 0.27 | 0.68 |
| Crushing strength, Newton/millimeter | 27.5 | 14.0 |
Table 3
| Embodiment | 1 | 2 | 3 | 4 |
| Processing condition | ||||
| The hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 3.2 | 3.2 |
| Temperature of reaction, ℃ | ||||
| First bed | 370 | 380 | 390 | 390 |
| Second bed | 240 | 240 | 240 | 240 |
| LHSV，h -1 | ||||
| First bed | 3.0 | 3.0 | 3.0 | 4.0 |
| Second bed | 6.0 | 6.0 | 6.0 | 8.0 |
| Total hydrogen-oil ratio, Nm 3/m 3 | 200 | 200 | 200 | 200 |
| Chemistry hydrogen consumption, % | 0.58 | 0.56 | 0.50 | 0.51 |
| Product property | ||||
| Density, g/cm 3 | 0.8246 | 0.8246 | 0.8248 | 0.8251 |
| Refractive index | 1.4632 | 1.4630 | 1.4642 | 1.4629 |
| S，ppm | 128.5 | 87 | 56 | 114 |
| Desulfurization degree, % | 98.7 | 99.1 | 99.4 | 98.9 |
| N，ppm | 12 | 9 | 7 | 15 |
| Total aromatic hydrocarbons, m% | 29.0 | 29.5 | 32.3 | 29.3 |
| Mononuclear aromatics | 20.3 | 19.8 | 20.1 | 19.1 |
| The above aromatic hydrocarbons of dicyclo | 8.1 | 9.0 | 11.4 | 9.8 |
| Boiling range (ASTM D86), ℃ | ||||
| Initial boiling point | 196 | 191 | 184 | 185 |
| 10％ | 238 | 235 | 231 | 233 |
| 30％ | 260 | 259 | 257 | 258 |
| 50％ | 271 | 270 | 268 | 269 |
| 70％ | 300 | 299 | 295 | 297 |
| 90％ | 349 | 347 | 342 | 344 |
| Do | 388 | 387 | 382 | 385 |
Table 4
| Embodiment | 5 | 6 | 7 | 8 |
| Processing condition | ||||
| The hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 6.4 | 6.4 |
| Temperature of reaction, ℃ | ||||
| First bed | 370 | 370 | 370 | 370 |
| Second bed | 260 | 280 | 280 | 280 |
| LHSV，h -1 | ||||
| First bed | 2.4 | 2.6 | 2.9 | 2.1 |
| Second bed | 5.6 | 6.0 | 6.7 | 5.0 |
| Total hydrogen-oil ratio, Nm 3/m 3 | 600 | 500 | 500 | 500 |
| Chemistry hydrogen consumption, % | 0.58 | 0.56 | 0.50 | 0.51 |
| Product property | ||||
| Density, g/cm 3 | 0.8836 | 0.8835 | 0.8846 | 0.8815 |
| Refractive index | 1.4961 | 1.4957 | 1.4968 | 1.4939 |
| S，ppm | 91 | 115 | 150 | 95 |
| Desulfurization degree, % | 98.4 | 97.9 | 97.3 | 98.3 |
| Total aromatic hydrocarbons, m% | 42.6 | 42.3 | 43.1 | 41.1 |
| Mononuclear aromatics | 19.2 | 19.2 | 19.6 | 18.8 |
| The above aromatic hydrocarbons of dicyclo | 23.4 | 23.1 | 23.5 | 22.3 |
| Boiling range (ASTM D86), ℃ | ||||
| Initial boiling point | 204 | 205 | 205 | 203 |
| 10％ | 238 | 239 | 240 | 238 |
| 30％ | 270 | 269 | 268 | 268 |
| 50％ | 295 | 295 | 294 | 294 |
| 70％ | 323 | 322 | 323 | 323 |
| 90％ | 351 | 351 | 352 | 351 |
| Do | 372 | 371 | 373 | 372 |
Table 5
| Embodiment | 9 | 10 | 11 | 12 |
| Processing condition | ||||
| The hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 4.8 | 4.8 |
| Temperature of reaction, ℃ | ||||
| First bed | 370 | 380 | 360 | 370 |
| Second bed | 280 | 280 | 280 | 280 |
| LHSV，h -1 | ||||
| First bed | 3.0 | 3.0 | 2.6 | 2.9 |
| Second bed | 4.5 | 4.5 | 6.0 | 6.7 |
| Total hydrogen-oil ratio, Nm 3/m 3 | 300 | 300 | 500 | 500 |
| Chemistry hydrogen consumption, % | 0.60 | 0.56 | 0.71 | 0.80 |
| Product property | ||||
| Density, g/cm 3 | 0.8252 | 0.8252 | 0.8221 | 0.8194 |
| Refractive index | 1.4605 | 1.4609 | 1.4574 | 1.4564 |
| S，ppm | 36 | 22 | 21 | 22 |
| Desulfurization degree, % | 99.7 | 99.8 | 99.8 | 99.8 |
| Total aromatic hydrocarbons, m% | 17.5 | 17.8 | 14.6 | 15.3 |
| Mononuclear aromatics | 13.2 | 13.4 | 10.9 | 11.5 |
| The above aromatic hydrocarbons of dicyclo | 4.3 | 4.4 | 3.7 | 3.8 |
| Boiling range (ASTM D86), ℃ | ||||
| Initial boiling point | 195 | 198 | 197 | 196 |
| 10％ | 244 | 240 | 245 | 244 |
| 30％ | 266 | 264 | 267 | 267 |
| 50％ | 278 | 276 | 278 | 279 |
| 70％ | 298 | 296 | 300 | 299 |
| 90％ | 334 | 333 | 336 | 336 |
| Do | 365 | 364 | 367 | 366 |
Claims (8)
1, a kind of process for deeply desulfurizing fractional oil of low hydrogen consumption is characterized in that diesel raw material contacts with Hydrobon catalyst in first bed with hydrogen, and reaction conditions is: hydrogen dividing potential drop 2.0～8.0MPa, 320～440 ℃ of temperature, liquid hourly space velocity are 2～7h
-1, total hydrogen-oil ratio 200～700Nm
3/ m
3, the effluent of first bed enters second bed without separation, contacts with hydrogen, Hydrobon catalyst, and reaction conditions is: hydrogen dividing potential drop 2.0～8.0MPa, temperature are that 200～290 ℃, liquid hourly space velocity are 4～10h
-1, reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and gas is through purifying, and rich hydrogenous gas circulation is returned reactor.
2,, it is characterized in that described diesel raw material is straight-run diesel oil, catalytic cracking diesel oil, coker gas oil or its mixture according to the method for claim 1.
3, according to the method for claim 1, it is characterized in that the reaction conditions of first bed: hydrogen dividing potential drop 3.0～6.5MPa, 350～400 ℃ of temperature, liquid hourly space velocity 3～5h
-1, total hydrogen-oil ratio 300～600Nm
3/ m
3
4, according to the method for claim 1, it is characterized in that the reaction conditions of second bed: hydrogen dividing potential drop 3.0～6.5MPa, 240～280 ℃ of temperature, liquid hourly space velocity 6～8h
-1
5, according to the method for claim 1, it is characterized in that the used Hydrobon catalyst of first bed and second bed is identical, this catalyzer can be VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.
6, according to the method for claim 1 or 5, it is characterized in that consisting of of described Hydrobon catalyst: 1～5 heavy % nickel oxide, 12～35 heavy % Tungsten oxide 99.999s, 1～9 heavy % fluorine and surplus aluminum oxide.
7, according to the method for claim 1, it is characterized in that adding the hydrogenation protecting agent at the Hydrobon catalyst top of first bed, the add-on of hydrogenation protecting agent is 1～20 volume % of Hydrobon catalyst.
8,, it is characterized in that described hydrogenation protecting agent is made up of the gamma-aluminium oxide carrier that diplopore distributes that has of 1.0～5.0 heavy % nickel oxide, 5.5～10.0 heavy % molybdenum oxides and surplus according to the method for claim 1.
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|---|---|---|---|---|
| CN1313573C (en) * | 2003-09-15 | 2007-05-02 | 中国石油化工股份有限公司 | Process for deep desulfating of diesel oil fractional oil |
| CN100448951C (en) * | 2005-08-09 | 2009-01-07 | 中国石油化工股份有限公司 | Method of producing catalytic reforming raw material |
| CN101376843B (en) * | 2007-08-27 | 2012-12-26 | 中国石油化工股份有限公司 | Method for reducing hydrogen consumption in liquid wax raw material hydrogenation |
-
2000
- 2000-11-28 CN CN 00132562 patent/CN1115387C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
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| CN1355273A (en) | 2002-06-26 |
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