CN103965959A - Liquid phase hydrogenation reaction method for multi-stage hydrogen dissolving - Google Patents
Liquid phase hydrogenation reaction method for multi-stage hydrogen dissolving Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 97
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000007791 liquid phase Substances 0.000 title claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 35
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000047 product Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000011344 liquid material Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 51
- 239000002283 diesel fuel Substances 0.000 description 11
- 239000012263 liquid product Substances 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000079 presaturation Methods 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a liquid phase hydrogenation reaction method of multi-stage dissolved hydrogen; mixing the circulating liquid material with the raw oil, and heating in a heating furnace; dividing hydrogen into n paths, and heating in a heating furnace; mixing one path of hydrogen and liquid phase materials in a mixer, carrying out first-stage hydrogen dissolution, mixing the rest (n-1) paths of hydrogen with a mixture obtained after the reaction of the previous bed layer through a hydrogen-oil mixing component in a reactor bed layer inlet, carrying out second-stage hydrogen dissolution, stripping out reaction by-products, namely hydrogen sulfide and ammonia, arranging a reaction pressure control system at the top of the reactor, and arranging an exhaust system at each section of the reactor; the reaction product enters a stripping tower, a hydrogen-oil mixer is arranged in the stripping tower, by-products of hydrogen sulfide and ammonia are stripped out, the hydrogen dissolving capacity is increased, part of the oil product discharged from the stripping tower enters a product tank, and part of the oil product is recycled; the method discharges hydrogen sulfide and ammonia out of the reaction system while catalyzing the hydrogenation reaction, and the solid-phase catalyst contacts with a liquid-phase reactant, so that the reaction efficiency is improved.
Description
Technical field
The present invention relates to a kind of liquid-phase hydrogenatin reaction method of multistage molten hydrogen, relate in particular to a kind of processing method of product circulation liquid-phase hydrogenatin processing.
Background technology
Along with people's environmental consciousness constantly strengthens, a lot of countries limit the sulphur content of diesel oil by environmental legislation, make it reach very low level (10 ~ 15 μ g/g), to reduce the discharge of obnoxious flavour, improve Air quality.The U.S. made the sulphur content in diesel oil be reduced to 15 μ g/g in 2006.Germany is reduced to 10 μ g/g in the January, 2003 by sulphur content.Other countries of European Union and Japan were reduced to 10 μ g/g in 2008 by sulphur content.China city motor diesel oil standard GB/T 19147-2009 formulates with reference to European III class standard, and its sulphur content requires to be less than 350 μ g/g.In the automobile-used petrol and diesel oil discharge index of five-stage that national environmental protection portion issues, diesel oil sulphur content requires to be less than 10 μ g/g.
World market diesel oil demand is in continuous growth, but high-grade stock oil supply is but reducing.How utilizing low-grade stock oil to produce ultra-low-sulphur diesel to meet growing demand, is the very large challenge that refinery has to face.For to cope with challenges, need to solve a gordian technique difficult problem on the one hand, newly-built hydrogenation unit carries out the deep hydrodesulfurizationof of diesel oil; Need again to reduce on the one hand in addition risk and overlapping investment to ensure economic benefit.In traditional trickle bed hydrogenation technique, hydrogen need to be delivered to liquid phase from gas phase, and then dissolved hydrogen and sulfocompound react in the active centre of catalyzer, thereby reaches desulfurization object.In this process, needed amounts of hydrogen is far longer than the amounts of hydrogen that hydrogenation reaction consumes.This is because on the one hand, hydrogenation reaction is a strong exothermal reaction, in order to control temperature of reaction, needs a large amount of hydrogen and stock oil to take away reaction heat by beds; On the one hand, in the reaction of gas-liquid-solid three-phase, maintain higher hydrogen dividing potential drop and be conducive to hydrogenation reaction in addition, suppress coke and generate, the extending catalyst life-span.In addition the hydrogen of, not participating in reaction is improved to be again transported to after pressure by circulating hydrogen compressor participates in reaction in reactor.Circulating hydrogen compressor is as the key equipment of hydrogenation process, and investment and process cost are higher.In order to cancel recycle hydrogen and circulating hydrogen compressor, reduce the cost of investment of device, liquid-phase hydrogenatin technology has been carried out, in liquid phase circulation hydrogenation technique, the first pre-mixing of hydrogen and stock oil, is dissolved in stock oil hydrogen, then enters reactor and react, in reaction process, required hydrogen is completely from the hydrogen dissolving, and without additionally filling into cold hydrogen.It is smaller that liquid phase circulation hydrogenation technique has reactor, cost of investment is low, the advantages such as the easy control of temperature of reaction, but, also there is a problem in liquid phase circulation hydrogenation, in order to meet needed amounts of hydrogen in hydrogenation process, need to or additionally add solvent to dissolve hydrogen with a large amount of turning oil, cause hydrogenation efficiency to reduce.
Generally contain the speed of reaction of raw material hydrogenating desulfurization in trickle bed hydrogenator of simple sulfide except having relation with the concentration of organic sulfide, be also subject to organic nitrogen compound and H in wetting situation, the reactor assembly of catalyzer
2the impact of the factors such as S concentration.The wetting factor of catalyzer is that catalyst surface under hydrogenation conditions is measured by the one of liquid reactants institute infiltration degree.The infiltration degree wetting factor higher, catalyzer of catalyzer is just higher, that is to say that the effective rate of utilization of catalyzer is higher.Under the definite condition of the factors such as catalyzer, the principal element that affects the catalyst irrigation factor is the flow velocity of liquid in reactor, and the ratio (hydrogen-oil ratio) of gas and flow rate of liquid.It is generally acknowledged, flow rate of liquid increases and strengthens catalyst irrigation effect, adopts the large hydrogen-oil ratio required considerably beyond reaction and conventional hydrogenation technique, thereby has reduced the wetting effect of catalyzer, and the wetting factor is had to adverse influence.In addition, in oil refining process, the investment of hydrogen recycle link accounts for the large percentage of whole process cost.
Organic nitrogen compound is the poisonous substance of hydrogenation catalyst, and hydrodenitrification, hydrogenating desulfurization and hydrogenation dearomatization reaction are had to obvious restraining effect.This supression effect is mainly to have very strong sorptive power due to the intermediate reaction product of some nitride and most of nitride and the hydrogenation reaction active centre of catalyzer, has restrained the carrying out of other hydrogenation reactions from the angle of competitive adsorption.And circulate the foreign matter content greatly diluting in raw material by hydrogenation products, be conducive to bring into play the performance of catalyzer.
Hydrogenating desulfurization by product H
2s also has obvious restraining effect to hydrodesulfurization reaction, hydrodenitrification and hydrogenation dearomatization reaction, document Sie S T.[J] .Reaction order and role of hydrogen sulfide in deephydrodesulfurization of gas oil:consequences for industrial reactorconfiguration, FuelProcessing Technology, 1999,61 (1-2): 149-171. think H
2s on hydrodesulfurization reaction affect one be make hydrodesulfurization reaction activation energy rise.Be hydrogenated to example with toluene, hydrogen sulfide sectional pressure is 0 o'clock, and reaction activity is 16kcal/mol, and in the time that hydrogen sulfide sectional pressure reaches 42kPa, activation energy rises to 20kcal/mol; Another impact is a small amount of H
2s exists will reduce hydrogenating desulfurization speed greatly, and H
2s is in the monolayer adsorption that is adsorbed as of catalyst surface, once adsorption center is by H
2s occupies, and speed of reaction will be no longer with H
2s dividing potential drop improves and declines.Therefore, adopt effective means to eliminate H
2the impact of S is the key issue that solves deep desulfuration.
US Patent No. 20060144756A1 discloses a kind of two-phase hydrogenation Controlling System method and apparatus.In continuous liquid-phase hydrogenatin process, cancel recycle hydrogen, the needed hydrogen of hydrogenation reaction all comes from the hydrogen of liquid phase dissolved, does not need extra hydrogen.But it need to dissolve hydrogen with the larger solvent of hydrogen solubility or thinner, affects follow-up hydrogenation efficiency.
US6213835, US6428686, CN200680018017.3 etc. disclose a kind of hydrogenation technique that dissolves in advance hydrogen, by controlling amount of liquid or the air pressure in the amounts of hydrogen control reactor in liquid feeding.But it does not solve the H producing in hydrofining reaction process completely
2s, NH
3the problem removing Deng detrimental impurity, causes it constantly in reactor, to accumulate, and greatly reduces reaction efficiency, also cannot effectively process sulphur, raw material that nitrogen content is higher, the also concrete structure of reactor openly not of above-mentioned document.
Summary of the invention
The object of this invention is to provide a kind of liquid-phase hydrogenatin reaction method of multistage molten hydrogen.
The liquid-phase hydrogenatin reaction method of multistage molten hydrogen of the present invention comprises following content: the part circulation that mixes the liquid material of hydrogen through stripping tower is mixed into liquid phase material with fresh feed oil, and liquid phase material enters process furnace heating; Hydrogen is divided into n road and enters process furnace heating, or is divided into n road after process furnace heating, and n equals the quantity of reactor catalyst bed or the quantity of staged reactor.Wherein a road hydrogen and oil product mix in mixing tank, carry out the molten hydrogen of the first step, all the other (n-1) road hydrogen enter hydrogen oil hybrid component in device by the entrance between reactor bed to be mixed with the reacted mixture of a upper bed, carry out the molten hydrogen in the second stage, stripping goes out byproduct of reaction hydrogen sulfide and ammonia simultaneously, every many beds or a reactor just increase the molten hydrogen of one-level, in reactor head, reaction pressure Controlling System is set, at every section of reactor, exhaust system is set, the liquid level of every section of reactor is by controlling the gas of next section of generation and the discharge of unnecessary hydrogen realizes.Reaction product enters stripping tower, and hydrogen oil mixing tank is set in stripping tower, and product can go out by product hydrogen sulfide and ammonia by stripping, increases dissolve hydrogen capacity simultaneously, and a stripping tower oil product part out enters products pot, a part of recirculation.
In the inventive method, the number n of the number of reactor catalyst bed or staged reactor is 3～5 grades.
In the inventive method, the liquid phase stream after dissolved hydrogen enters reactor from liquid phase circulation hydrogenator top, flows out from reactor lower part; Or liquid phase stream enters reactor from liquid phase circulation hydrogenator bottom, flow out from reactor top.
In the inventive method, hydrogen oil hybrid component is set in reactor.
In the inventive method, hydrogen oil mixing tank is set in stripping tower, hydrogen oil hybrid component also can be set.
In the inventive method, catalyst bed hydrogen to oil volume ratio is 2 ︰ 1～10 ︰ 1.
In the inventive method, determine the blending ratio of turning oil and stock oil according to the stability of the needed hydrogen amount of reaction and beds, with the hydrogen amount that ensures to dissolve in mixture.Utilize the ratio control of stock oil and turning oil to enter the temperature of reactor.In the time that chemical hydrogen consumption is high and reaction heat is higher, suitably improve circulation oil mass, otherwise reduce the amount of turning oil.The volume ratio of turning oil and raw material is 0.1 ︰ 1～5 ︰ 1, and catalyst bed hydrogen to oil volume ratio is 2 ︰ 1～10 ︰ 1.
A kind of liquid-phase hydrogenation processing method with multistage molten hydrogen system of the present invention and reactive system are the two-phase hydrogenation reactions of carrying out in fixed-bed reactor, and reacting needed hydrogen is provided by the excess hydrogen of dissolving in stock oil.Hydrogenation technique condition requires to determine according to the character of raw material, end product quality.In general, temperature of reaction is at 220～420 DEG C, and reactive hydrogen dividing potential drop is 0.5～15MPa, and volume space velocity is 0.8～15h
-1.
Hydrogenator of the present invention has catalytic hydrogenation reaction simultaneously and byproduct of reaction hydrogen sulfide and ammonia is discharged to the effect of reactive system function, and what contact with solid-phase catalyst is liquid phase reacting material, thereby has improved hydrogenation reaction efficiency.
The present invention is mainly used in deep desulfuration, denitrogenation, the de-aromatic hydrocarbons of poor ignition quality fuel component, produce clean diesel, also can be used for the hydrofining production high-quality oil products such as petroleum naphtha, boat coal, lubricating oil, paraffin, and for the clean boat of wax oil raw material mild hydrocracking production high-quality coal, diesel oil technological process.
Brief description of the drawings
Fig. 1 is a kind of liquid-phase hydrogenation processing method with multistage molten hydrogen system of the present invention and reactive system schema.
In figure: 1-stock oil, 2-turning oil, 3-hydrogen, 4-process furnace, 5-mixing tank, 6-reactor, 7-pressure controlled valve, 8/13/14/15/18-gas-phase product, 9/10/11/12-level control valve, 16-liquid-phase reaction product, 17-stripping tower, 19-stripping gas, 20-recycle pump, 21-product
Embodiment
As shown in Figure 1, fresh feed oil 1 and turning oil 2 enter mixing tank 5 and are mixed to form presaturation liquid phase stream from process furnace 4 hydrogen 3 out after process furnace 4 heating, presaturation liquid phase stream enters the many bed reactors of single-stage or multistage hydrogenator 6 carries out hydrogenation reaction, and in reaction, gas-phase product 8/13/14/15/18 is discharged reactor.Liquid-phase reaction product 16 enters stripping tower 17, and after stripping gas 19 strippings, gas-phase product 18 is discharged through tower top, and the liquid product part after stripping enters process furnace 4 through recycle pump 20 as turning oil 2.Another part liquid product enters products pot with the form of product 21.In reactor head, reaction pressure control valve 7 is set, at every section of reactor, exhaust system level control valve 9/10/11/12 is set.
The following examples illustrate the present invention further.
Experiment is used the hydrotreating catalyst that catalyzer is industrial application, for PHF-101 diesel hydrogenation for removal sulphur catalyst, PHT-01 heavy-oil hydrogenation pretreatment catalyst, the SD-2 hydrogenation catalyst of the development and production of Petroleum Chemical Engineering Institute of CNPC, its physico-chemical property index is in table 1.
Embodiment 1
Medium diesel oil reaches temperature required through process furnace and in gas liquid mixer, after abundant mixed dissolution, enters hydrogenator with hydrogen, and reaction conditions is: 310 DEG C of hydrogen dividing potential drop 6.5MPa, temperature of reaction, hydrogen to oil volume ratio is 300:1.Liquid product enters stripping tower and carries out stripping, and the liquid product part after stripping enters process furnace through recycle pump as turning oil, and another part liquid product enters products pot with the form of product.Stock oil character and product property are listed in table 2.
From table 2, adopt this Technology can make sulphur, nitrogen content in diesel oil obviously reduce.
Embodiment 2
Heavy wax oil raw material reaches temperature required through process furnace and in gas liquid mixer, after abundant mixed dissolution, enters hydrogenator with hydrogen, and reaction conditions is: 365 DEG C of hydrogen dividing potential drop 12.0MPa, temperature of reaction, hydrogen to oil volume ratio is 800:1.Liquid product enters stripping tower and carries out stripping, and the liquid product part after stripping enters process furnace through recycle pump as turning oil, and another part liquid product enters products pot with the form of product.Stock oil character and product property are listed in table 3.
From table 3, adopt this Technology can make the sulphur nitrogen impurity content in pyroparaffine oil obviously reduce.
Embodiment 3
Scale wax raw material reaches temperature required through process furnace and in gas liquid mixer, after abundant mixed dissolution, enters hydrogenator with hydrogen, and reaction conditions is: 240 DEG C of hydrogen pressure component 7.0MPa, temperature of reaction, hydrogen to oil volume ratio is 400:1.Liquid product enters stripping tower and carries out stripping, and the liquid product part after stripping enters process furnace through recycle pump as turning oil, and another part liquid product enters products pot with the form of product.Stock oil character and product property are listed in table 4.
From table 4, adopt this Technology can improve color and the light stability of paraffin wax product.
Comparative example 1
Process the Medium diesel oil of same nature, adopt the correlation data of present method and ordinary method in table 5.As can be seen from Table 5, present method temperature of reaction is low 16 DEG C compared with ordinary method, and hydrogen-oil ratio is only 300, be 3/5ths of ordinary method, and product property is better than ordinary method.
The physico-chemical property index of table 1 catalyzer
| Catalyzer numbering | PHF-101 | PHT-01 | SD-2 |
| Metal composition | |||
| WO 3 | 25.1 | --- | 26.4 |
| MoO 3 | --- | 20～30 | --- |
| NiO | 3.2 | 3～10 | 3.3 |
| Pore volume, mL/g | ≮0.37 | ≮0.33 | ≮0.35 |
| Specific surface area, m 2/g | ≮150 | ≮160 | ≮190 |
| Shape | Trifolium | Trifolium | Trifolium |
Table 2 embodiment 1 stock oil character and test-results
Table 3 embodiment 2 stock oil character and test-results
Table 4 embodiment 3 stock oil character and test-results
Table 5 comparative example 1 stock oil character and test-results
Claims (7)
1. the liquid-phase hydrogenatin reaction method of a multistage molten hydrogen, it is characterized in that: the method comprises: the part circulation that mixes the liquid material of hydrogen through stripping tower is mixed into liquid phase material with fresh feed oil, and liquid phase material enters process furnace heating, hydrogen is divided into n road and enters process furnace heating, or is divided into n road after process furnace heating, and n equals the quantity of reactor catalyst bed or the quantity of staged reactor, wherein a road hydrogen and liquid phase material mix in mixing tank, carry out the molten hydrogen of the first step, all the other (n-1) road hydrogen enter hydrogen oil hybrid component in device by the entrance between reactor bed to be mixed with the reacted mixture of a upper bed, carry out the molten hydrogen in the second stage, stripping goes out byproduct of reaction hydrogen sulfide and ammonia simultaneously, every many beds or a reactor just increase the molten hydrogen of one-level, in reactor head, reaction pressure Controlling System is set, at every section of reactor, exhaust system is set, the liquid level of every section of reactor is by controlling the gas of next section of generation and the discharge of unnecessary hydrogen realizes, reaction product enters stripping tower, and hydrogen oil mixing tank is set in stripping tower, and stripping goes out by product hydrogen sulfide and ammonia, increases dissolve hydrogen capacity simultaneously, and a stripping tower oil product part out enters products pot, a part of recirculation.
2. the liquid-phase hydrogenatin reaction method of multistage molten hydrogen according to claim 1, is characterized in that: n is 3～5 grades.
3. the liquid-phase hydrogenatin reaction method of multistage molten hydrogen according to claim 1, is characterized in that: the liquid phase stream after dissolved hydrogen enters reactor from liquid phase circulation hydrogenator top, flows out from reactor lower part; Or liquid phase stream enters reactor from liquid phase circulation hydrogenator bottom, flow out from reactor top.
4. the liquid-phase hydrogenatin reaction method of multistage molten hydrogen according to claim 1, is characterized in that: hydrogen oil hybrid component is set in reactor.
5. the liquid-phase hydrogenatin reaction method of multistage molten hydrogen according to claim 1, is characterized in that: hydrogen oil mixing tank is set in stripping tower, or hydrogen oil hybrid component is set.
6. the liquid-phase hydrogenatin reaction method of multistage molten hydrogen according to claim 1, is characterized in that: catalyst bed hydrogen to oil volume ratio is 2 ︰ 1～10 ︰ 1.
7. the liquid-phase hydrogenatin reaction method of multistage molten hydrogen according to claim 1, is characterized in that: the volume ratio of turning oil and raw material is 0.1 ︰ 1～5 ︰ 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310035274.XA CN103965959A (en) | 2013-01-30 | 2013-01-30 | Liquid phase hydrogenation reaction method for multi-stage hydrogen dissolving |
| SG11201505262PA SG11201505262PA (en) | 2013-01-30 | 2013-08-01 | Liquid-phase hydrogenation reaction method with multi-stage hydrogen dissolution |
| PCT/CN2013/000903 WO2014117309A1 (en) | 2013-01-30 | 2013-08-01 | Liquid-phase hydrogenation reaction method for multi-stage hydrogen dissolution |
| ZA2015/06228A ZA201506228B (en) | 2013-01-30 | 2015-08-26 | Liquid-phase hydrogenation reaction method with multi-stage hydrogen dissolution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310035274.XA CN103965959A (en) | 2013-01-30 | 2013-01-30 | Liquid phase hydrogenation reaction method for multi-stage hydrogen dissolving |
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| CN201310035274.XA Pending CN103965959A (en) | 2013-01-30 | 2013-01-30 | Liquid phase hydrogenation reaction method for multi-stage hydrogen dissolving |
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| Country | Link |
|---|---|
| CN (1) | CN103965959A (en) |
| SG (1) | SG11201505262PA (en) |
| WO (1) | WO2014117309A1 (en) |
| ZA (1) | ZA201506228B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602619A (en) * | 2015-12-18 | 2016-05-25 | 中国石油天然气股份有限公司 | Liquid-phase hydrogenation isomerization system and process and application thereof |
| CN105713656A (en) * | 2014-12-01 | 2016-06-29 | 中国石油天然气股份有限公司 | Micro-bubble intra-reactor hydrogen dissolving reactor and application method thereof |
| CN105778994A (en) * | 2016-03-25 | 2016-07-20 | 中国海洋石油总公司 | Combined process method for producing ultra-low-sulfur diesel |
| CN106590732A (en) * | 2015-10-15 | 2017-04-26 | 神华集团有限责任公司 | Method and system for low temperature liquid phase hydrofinishing of Fischer-Tropsch syncrude |
| CN109679682A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of molten hydrogen storage equipment and molten hydrogen methods |
| CN110643390A (en) * | 2019-08-22 | 2020-01-03 | 中科合成油工程股份有限公司 | Hydrogenation method of high-reactivity oil product |
| CN115466628A (en) * | 2021-06-10 | 2022-12-13 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation reaction device and system and hydrocarbon oil liquid-phase hydrogenation method |
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| CN105623727B (en) * | 2014-10-28 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of hydrofinishing process for producing ultra-low-sulphur diesel |
| CN105623726B (en) * | 2014-10-28 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method of hydrotreating for producing diesel oil |
| US11208600B2 (en) | 2019-12-04 | 2021-12-28 | Saudi Arabian Oil Company | Mixed phase two-stage hydrotreating processes for enhanced desulfurization of distillates |
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| CN105713656A (en) * | 2014-12-01 | 2016-06-29 | 中国石油天然气股份有限公司 | Micro-bubble intra-reactor hydrogen dissolving reactor and application method thereof |
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| CN106590732A (en) * | 2015-10-15 | 2017-04-26 | 神华集团有限责任公司 | Method and system for low temperature liquid phase hydrofinishing of Fischer-Tropsch syncrude |
| CN106590732B (en) * | 2015-10-15 | 2019-04-09 | 神华集团有限责任公司 | A kind of method and system for low-temperature liquid-phase hydrorefining of Fischer-Tropsch synthetic oil |
| US10683459B2 (en) | 2015-12-18 | 2020-06-16 | Petrochina Company Limited | Liquid-phase hydroisomerization system and process therefor and use thereof |
| CN105602619A (en) * | 2015-12-18 | 2016-05-25 | 中国石油天然气股份有限公司 | Liquid-phase hydrogenation isomerization system and process and application thereof |
| CN105778994A (en) * | 2016-03-25 | 2016-07-20 | 中国海洋石油总公司 | Combined process method for producing ultra-low-sulfur diesel |
| CN109679682A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of molten hydrogen storage equipment and molten hydrogen methods |
| CN109679682B (en) * | 2017-10-19 | 2020-09-11 | 中国石油化工股份有限公司 | Hydrogen dissolving equipment and hydrogen dissolving method |
| CN110643390A (en) * | 2019-08-22 | 2020-01-03 | 中科合成油工程股份有限公司 | Hydrogenation method of high-reactivity oil product |
| CN110643390B (en) * | 2019-08-22 | 2021-10-22 | 中科合成油工程有限公司 | Hydrogenation method of high-reactivity oil product |
| CN115466628A (en) * | 2021-06-10 | 2022-12-13 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation reaction device and system and hydrocarbon oil liquid-phase hydrogenation method |
| CN115466628B (en) * | 2021-06-10 | 2023-12-12 | 中国石油化工股份有限公司 | Liquid phase hydrogenation reaction device and system and hydrocarbon oil phase hydrogenation method |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA201506228B (en) | 2019-07-31 |
| WO2014117309A1 (en) | 2014-08-07 |
| SG11201505262PA (en) | 2015-08-28 |
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