CN106748613A - A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel - Google Patents
A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel Download PDFInfo
- Publication number
- CN106748613A CN106748613A CN201710040319.0A CN201710040319A CN106748613A CN 106748613 A CN106748613 A CN 106748613A CN 201710040319 A CN201710040319 A CN 201710040319A CN 106748613 A CN106748613 A CN 106748613A
- Authority
- CN
- China
- Prior art keywords
- hexadecane
- crystalline state
- support type
- state catalyst
- type crystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 title claims abstract description 110
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 36
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 claims description 24
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 13
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 claims description 12
- KUVMKLCGXIYSNH-UHFFFAOYSA-N isopentadecane Natural products CCCCCCCCCCCCC(C)C KUVMKLCGXIYSNH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- -1 nickel hexadecane Chemical compound 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000012188 paraffin wax Substances 0.000 abstract description 7
- 231100000614 poison Toxicity 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000002574 poison Substances 0.000 abstract description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 241000269350 Anura Species 0.000 abstract 1
- 206010013786 Dry skin Diseases 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003225 biodiesel Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 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
- 239000002028 Biomass Substances 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/13—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation with simultaneous isomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel.The invention belongs to heavy paraffin hydrocarbon isomerization field, and in particular to a kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel.The invention aims to solve the problems, such as to be used in the prior art the high cost containing noble metal catalyst of Long carbon chain heavy paraffin hydrocarbon isomerization, halophile poison poor performance and isomerization catalyst without noble metal selectivity it is low.Method:By Ni (NO3)2·6H2O and (NH4)2HPO4Water is dissolved in, the molecular sieves of SAPO 31 are added, is 100 DEG C of dryings in temperature, be subsequently placed in Muffle kiln roasting, then temperature programmed reduction in a hydrogen atmosphere, obtain catalyst, loading catalyst carries out hexadecane hygrogenating isomerization reaction in the reactor.
Description
Technical field
The invention belongs to heavy paraffin hydrocarbon isomerization field, and in particular to positive ten on a kind of support type crystalline state catalyst of phosphatizing nickel
The method of six alkane hygrogenating isomerization reactions.
Background technology
In recent years, as the progress of Global Auto industrial expansion and engine technology, particularly world wide are interior to ring
The continuous improvement of guaranteed request, to low aromatic hydrocarbons and olefin(e) centent and has the environment-friendly alkylation fuel oil of good performance
Demand increasingly increase.Normal paraffin content is to reduce its solidification in reducing diesel oil with traditional solvent dewaxing and cracking dewaxing
The method of point is compared, and is converted into by n-alkane (wax) the hydrogenated isomerization reaction in the distillate that obtains petroleum refining
Branched paraffin is the low condensation point fuel oil most efficient method of production.
On the other hand, disappear with fuel oil as the non-renewable resources amount in global range with oil as representative is increasingly reduced
The ever-increasing imbalance between supply and demand of expense amount becomes increasingly conspicuous, and the development and application of the reproducible bio-fuel technology of resource has caused the world
The most attention of many countries.Biodiesel as one of main bio-fuel, due to raw material resources recyclability, producing
The advantages of product environmental protection, the in recent years exploitation of its new process for producing, new technology and new product has turned into worldwide research heat
Point.It is being produced by catalytic hydrogenation process as raw material with vegetable oil, with C15~C18Isoparaffin is given birth to for the second generation of main component
Thing diesel oil is referred to as green diesel, and its performance is substantially better than the first generation biodiesel with fatty acid methyl ester as main component, low
Warm good fluidity, Cetane number is high, and energy density is high, can be adjusted with arbitrary proportion with petroleum based diesel in low temperature environment
Match somebody with somebody, be one of main development direction of future biological fuel producing technology.Add in two kinds of production technologies of second generation biodiesel
Hydrogen deoxidation isomerization processes have more application prospect, the first stage be the biomass materials such as vegetable oil hydrogenation deoxidation technique relatively into
Ripe, second stage is the deoxidation oil (C for obtaining the first stage15~C18It is the n-alkane of main component) hysomer, by
Be susceptible to cracking reaction in the Long carbon chain n-alkane in isomerization reaction, thus reduce isoparaffin selectivity and
The liquid yield of diesel oil, therefore, efficient hygrogenating isomerization reaction catalyst is developed to suppress cracking reaction generation, keeping good
The selectivity that Long carbon chain n-alkane hygrogenating isomerization reaction is improved on the basis of catalysis activity is production high-quality, environment-friendly
The key of type second generation biodiesel.
Bifunctional catalyst with suitable metal position and acidic site is the heavy paraffin hydrocarbon hygrogenating isomerization reaction of Long carbon chain
Realize the key of high selectivity.The noble metals such as Pt and Pd are the catalyst of metal active position because production cost is high, resistant to sulfur nitrification
The ability that thing poisons, its application is subject to certain restrictions.The metal sulfides such as Ni-Co, Ni-W, Ni-Mo are urging for metal position
The selectivity of the hygrogenating isomerization reaction of agent is relatively low, causes cracking reaction to aggravate, and the liquid yield of diesel oil is relatively low in product.Cause
This, there is provided it is a kind of to there is high isomerization selectivity without noble metal, to the n-alkane of Long carbon chain, can be used to produce second generation life
The efficient bifunctional catalyst of thing diesel oil, will solve existing catalyst and is difficult to while having high selectivity, low cost, resistant to sulfur nitridation concurrently
The technical barrier that thing poisons.
The content of the invention
The invention aims to solve to be used for being urged containing noble metal for Long carbon chain heavy paraffin hydrocarbon isomerization in the prior art
The high cost of agent, halophile poison the low problem of selectivity of poor performance and the isomerization catalyst without noble metal,
And the method that hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel is provided.
On a kind of support type crystalline state catalyst of phosphatizing nickel of the invention the method for hexadecane hygrogenating isomerization reaction press with
Lower step is carried out:
The support type crystalline state catalyst of phosphatizing nickel of 20~40 mesh is loaded into the flat-temperature zone of fixed bed isothermal reactor, in temperature
It is that 400~500 DEG C and hydrogen flow rate are to activate 20min~100min under conditions of 20mL/min~80mL/min to spend, and is then adopted
Hexadecane is injected into fixed bed isothermal reactor with the mode that is continuously injected into, is 280~420 DEG C, reaction in reaction temperature
Pressure is 1MPa~4MPa, hexadecane mass space velocity is 1h-1~4h-1With the volume ratio of hydrogen and hexadecane for 300~
800:Reacted under conditions of 1, obtained isohexadecane;
The support type crystalline state catalyst of phosphatizing nickel is the molecular sieve carried crystalline state catalyst of phosphatizing nickel of SAPO-31.
The beneficial effects of the invention are as follows:
1st, class noble metal nickel phosphide has low cost, the tolerance to poisonous substances such as sulfide as the metal position of catalyst
It is good, not easy-sintering, the advantages of reactivity is higher.
2nd, there is gentle acid and suitable pore passage structure as the SAPO-31 molecular sieves of double-function catalyzing agent carrier,
There is isomerisation selectivity and good resistance to carbon distribution performance high to the hygrogenating isomerization reaction of n-alkane.
3rd, hexadecane hygrogenating isomerization reaction has reactivity and isomerization on support type crystalline state catalyst of phosphatizing nickel
The characteristics of high, the resistance to carbon distribution of selectivity and halophile poison excellent performance, is a kind of biological by hygrogenating isomerization reaction production
The effective ways of diesel oil and clean fuel oil.
Brief description of the drawings
Fig. 1 is the XRD spectrums for testing the SAPO-31 molecular sieves in;
Fig. 2 is the stereoscan photograph for testing the SAPO-31 molecular sieves in;
Fig. 3 is the transmission electron microscope photo for testing support type crystalline state catalyst of phosphatizing nickel in.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, also including each specific embodiment it
Between any combination.
Specific embodiment one:Hexadecane hydrogenation is different on a kind of support type crystalline state catalyst of phosphatizing nickel of present embodiment
The method of structureization reaction is carried out according to the following steps:
The support type crystalline state catalyst of phosphatizing nickel of 20~40 mesh is loaded into the flat-temperature zone of fixed bed isothermal reactor, in temperature
It is that 400~500 DEG C and hydrogen flow rate are to activate 20min~100min under conditions of 20mL/min~80mL/min to spend, and is then adopted
Hexadecane is injected into fixed bed isothermal reactor with the mode that is continuously injected into, is 280~420 DEG C, reaction in reaction temperature
Pressure is 1MPa~4MPa, hexadecane mass space velocity is 1h-1~4h-1With the volume ratio of hydrogen and hexadecane for 300~
800:Reacted under conditions of 1, obtained isohexadecane;
The support type crystalline state catalyst of phosphatizing nickel is the molecular sieve carried crystalline state catalyst of phosphatizing nickel of SAPO-31.
Specific embodiment two:Present embodiment from unlike specific embodiment one:The SAPO-31 molecular sieves are
With circular one-dimensional linear pore passage structure, acid gentle SAPO-31 molecular sieves.Other are identical with specific embodiment one.
Specific embodiment three:Present embodiment from unlike specific embodiment one or two:The SAPO-31 molecules
The mass ratio for sieving nickel phosphide and SAPO-31 molecular sieves in the crystalline state catalyst of phosphatizing nickel of load is 3~8:100, and metal active
111 crystal faces of the position dropping place in nickel phosphide crystal.Other are identical with specific embodiment one or two.
Specific embodiment four:Unlike one of present embodiment and specific embodiment one to three:The SAPO-31
Nickel phosphide and the mass ratio of SAPO-31 molecular sieves are 3~5 in molecular sieve carried crystalline state catalyst of phosphatizing nickel:100.Other with
One of specific embodiment one to three is identical.
Specific embodiment five:Unlike one of present embodiment and specific embodiment one to four:The SAPO-31
Nickel phosphide and the mass ratio of SAPO-31 molecular sieves are 4 in molecular sieve carried crystalline state catalyst of phosphatizing nickel:100 other with it is specific
One of implementation method one to four is identical.
Specific embodiment six:Unlike one of present embodiment and specific embodiment one to five:It is 440 in temperature
DEG C and hydrogen flow rate be 40mL/min under conditions of activate 60min.Other are identical with one of specific embodiment one to five.
Specific embodiment seven:Unlike one of present embodiment and specific embodiment one to six:The reaction temperature
Spend is 300~370 DEG C.Other are identical with one of specific embodiment one to six.
Specific embodiment eight:Unlike one of present embodiment and specific embodiment one to seven:The reaction temperature
Spend is 330 DEG C.Other are identical with one of specific embodiment one to seven.
Specific embodiment nine:Unlike one of present embodiment and specific embodiment one to eight:The reaction pressure
Power is 2MPa~3MPa.Other are identical with one of specific embodiment one to eight.
Specific embodiment ten:Present embodiment from unlike specific embodiment one to nine:The hexadecane matter
Amount air speed is 2h-1~3h-1.Other are identical with one of specific embodiment one to ten.
Specific embodiment 11:Unlike one of present embodiment and specific embodiment one to ten:The hydrogen
It is 400~600 with the volume ratio of hexadecane:1.Other are identical with one of specific embodiment one to ten.
Specific embodiment 12:Present embodiment from unlike specific embodiment one to one of 11:The hydrogen
Gas is 500 with the volume ratio of hexadecane:1.Other are identical with specific embodiment one to one of 11.
Using following examples and contrast experiment's checking beneficial effects of the present invention:
The side of hexadecane hygrogenating isomerization reaction in a kind of experiment one, support type crystalline state catalyst of phosphatizing nickel of this experiment
Method is carried out according to the following steps:
The support type crystalline state catalyst of phosphatizing nickel of 20~40 mesh is loaded into the flat-temperature zone of fixed bed isothermal reactor, in temperature
Spend is that 440 DEG C and hydrogen flow rate are used to activate 60min under conditions of 40mL/min, then and be continuously injected into mode by hexadecane
Be injected into fixed bed isothermal reactor, reaction temperature be 350 DEG C, reaction pressure be that 2MPa, hexadecane mass space velocity are
2.78h-1It is 500 with the volume ratio of hydrogen and hexadecane:Reacted under conditions of 1, obtained isohexadecane;
The support type crystalline state catalyst of phosphatizing nickel is the molecular sieve carried crystalline state catalyst of phosphatizing nickel of SAPO-31.
SAPO-31 described in this experiment molecular sieve carried crystalline state catalyst of phosphatizing nickel preparation method is as follows:
First, by Ni (NO3)2·6H2O and (NH4)2HPO4Water is dissolved in, pH value is then adjusted to 4.5, settled solution is obtained;
Ni (NO described in step one3)2·6H2O and (NH4)2HPO4Middle Ni/P mol ratios are 1.1:1;
Ni (NO described in step one3)2·6H2O is 1.1 with the mass ratio of water:10;
2nd, the SAPO-31 molecular sieves after roasting membrane removal are added in the settled solution for obtaining to step one, after being well mixed
Temperature obtains catalyst powder to dry 6h under conditions of 100 DEG C;
Ni (NO in settled solution described in step 23)2·6H2O and the SAPO-31 molecular sieves being calcined after membrane removal
Mass ratio is 19.8:100;
3rd, the catalyst powder that step 2 is obtained is placed in Muffle furnace, 5h is calcined under conditions of 510 DEG C of temperature, then
Go in tube furnace, heating reduction is carried out in a hydrogen atmosphere, obtain the molecular sieve carried crystalline state nickel phosphide catalysis of SAPO-31
Agent, i.e. support type crystalline state catalyst of phosphatizing nickel;The weight/mass percentage composition that wherein nickel phosphide accounts for SAPO-31 is 4%;
Described heating reduction process is:First with the speed of 10 DEG C/min by room temperature to 240 DEG C, then with 2 DEG C/
The speed of min is warming up to 640 DEG C by 240 DEG C, and 3h is kept under conditions of being then 640 DEG C in temperature.
(1) X-ray diffraction sign is carried out to the SAPO-31 molecular sieves, obtains SAPO-31 molecular sieves as shown in Figure 1
XRD spectra, it will be seen from figure 1 that being to occur in that and opened up corresponding to ATO at 8.52 °, 20.29 °, 22.05 ° and 22.67 ° in 2 θ
The characteristic diffraction peak of structure is flutterred, and without other diffraction maximums, illustrates the SAPO-31 molecular sieves for pure phase.
(2) Electronic Speculum sign is scanned to the SAPO-31 molecular sieves, SAPO-31 molecular sieves as shown in Figure 2 are obtained
SEM photograph, figure it is seen that the aggregation pattern of SAPO-31 molecular sieves, for bar-shaped, length is about 3 μm, and diameter is about 1
μm。
(3) transmission electron microscope sign is carried out to the support type crystalline state catalyst of phosphatizing nickel, obtains load as shown in Figure 3
The TEM photos of type crystalline state catalyst of phosphatizing nickel, from figure 3, it can be seen that nickel phosphide is homogeneously dispersed in SAPO-31 molecular sieve tables
Face, and it is the lattice fringe of 0.22nm the interplanar distance of 111 crystal faces of correspondence occur, illustrates that metal active position dropping place is brilliant in nickel phosphide
111 crystal faces of body.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment one is
67.2%, the selectivity and yield of isohexadecane are respectively 89.9% and 60.4%.
Test two, this experiment and test unlike one:In the support type crystalline state catalyst of phosphatizing nickel preparation method:Step
Ni (NO in settled solution in rapid two3)2·6H2O is 14.8 with the mass ratio of the SAPO-31 molecular sieves being calcined after membrane removal:100, step
The weight/mass percentage composition that nickel phosphide in the molecular sieve carried crystalline state catalyst of phosphatizing nickel of SAPO-31 accounts for SAPO-31 is obtained in rapid three
It is 3%.Hexadecane is injected into fixed bed isothermal reactor using the mode that is continuously injected into.Other reaction conditions and experiment one
It is identical.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment two is
The selectivity and yield of 72.5% isohexadecane are respectively 86.5% and 62.7%.
Test three, this experiment and test unlike one:In the support type crystalline state catalyst of phosphatizing nickel preparation method:Step
Ni (NO in rapid two in settled solution3)2·6H2O is 24.8 with the mass ratio of the SAPO-31 molecular sieves being calcined after membrane removal:100,
Obtain nickel phosphide in the molecular sieve carried crystalline state catalyst of phosphatizing nickel of SAPO-31 in step 3 and account for the quality percentage of SAPO-31 containing
Measure is 5%.Other reaction conditions are identical with experiment one.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment three is
47.9%, the selectivity and yield of isohexadecane are respectively 82.4% and 39.5%.
Test four, this experiment and test unlike one:Hexadecane is injected into fixed bed using mode is continuously injected into
In isothermal reactor, reacted at being 330 DEG C in reaction temperature.Other reaction conditions are identical with experiment one.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment four is
The selectivity and yield of 43.4% isohexadecane are respectively 82.7 and 35.9%.
Test five, this experiment and test unlike one:Hexadecane is injected into fixed bed using mode is continuously injected into
In isothermal reactor, reacted at being 370 DEG C in reaction temperature.Other reaction conditions are identical with experiment one.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment five is
88.5%, the selectivity and yield of isohexadecane are respectively 87.2% and 77.1%.
Test six, this experiment and test unlike one:Hexadecane is injected into fixed bed using mode is continuously injected into
In isothermal reactor, reacted in the case where reaction pressure is 4MPa.Other reaction conditions are identical with experiment one.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment six is
60.8%, the selectivity and yield of isohexadecane are respectively 81.3% and 49.4%.
Test seven, this experiment and test unlike one:Hexadecane is injected into fixed bed using mode is continuously injected into
It is 2h in hexadecane mass space velocity in isothermal reactor-1Under reacted.Other reaction conditions are identical with experiment one.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment seven is
78.7%, the selectivity and yield of isohexadecane are respectively 80.6% and 63.4%.
Test eight, this experiment and test unlike one:Hexadecane is injected into fixed bed using mode is continuously injected into
It is 3.69h in hexadecane mass space velocity in isothermal reactor-1Under reacted.Other reaction conditions are identical with experiment one.
Using the composition of gas chromatographic analysis hydroisomerised product, the conversion ratio for obtaining hexadecane in experiment eight is
59.4%, the selectivity and yield of isohexadecane are respectively 86.1% and 51.1%.
(1) carry out physico-chemical property to the support type crystalline state catalyst of phosphatizing nickel in experiment one to eight to characterize, as a result see
Table 1.
The physico-chemical property of the support type crystalline state catalyst of phosphatizing nickel of table 1
(2) hexadecane hygrogenating isomerization reaction on the support type crystalline state catalyst of phosphatizing nickel obtained to experiment one to eight
Condition and result are summarized, and are listed in table 2.
Hexadecane hygrogenating isomerization reaction result on the support type crystalline state catalyst of phosphatizing nickel of table 2
Claims (10)
1. on a kind of support type crystalline state catalyst of phosphatizing nickel hexadecane hygrogenating isomerization reaction method, it is characterised in that the party
Method is carried out according to the following steps:
The support type crystalline state catalyst of phosphatizing nickel of 20~40 mesh is loaded into the flat-temperature zone of fixed bed isothermal reactor, is in temperature
400~500 DEG C is activation 20min~100min under conditions of 20mL/min~80mL/min with hydrogen flow rate, then using company
Be injected into hexadecane in fixed bed isothermal reactor by continuous injection mode, is 280~420 DEG C, reaction pressure in reaction temperature
For 1MPa~4MPa, hexadecane mass space velocity are 1h-1~4h-1It is 300~800 with the volume ratio of hydrogen and hexadecane:1
Under conditions of reacted, obtain isohexadecane;
The support type crystalline state catalyst of phosphatizing nickel is the molecular sieve carried crystalline state catalyst of phosphatizing nickel of SAPO-31.
2. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that described SAPO-31 molecular sieves are gentle with circular one-dimensional linear pore passage structure, acidity
SAPO-31 molecular sieves.
3. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that nickel phosphide and SAPO-31 molecular sieves in the SAPO-31 molecular sieve carried crystalline state catalyst of phosphatizing nickel
Mass ratio be 3~8:100, and metal active position dropping place is in 111 crystal faces of nickel phosphide crystal.
4. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that activate 60min under conditions of temperature is 440 DEG C and hydrogen flow rate is 40mL/min.
5. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that the reaction temperature is 300~370 DEG C.
6. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that the reaction temperature is 350 DEG C.
7. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that the reaction pressure is 2MPa~3MPa.
8. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that the hexadecane mass space velocity is 2h-1~3h-1。
9. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that the hydrogen is 400~600 with the volume ratio of hexadecane:1.
10. hexadecane hygrogenating isomerization reaction on a kind of support type crystalline state catalyst of phosphatizing nickel according to claim 1
Method, it is characterised in that the volume ratio of the hydrogen and hexadecane is 500:1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710040319.0A CN106748613B (en) | 2017-01-19 | 2017-01-19 | A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710040319.0A CN106748613B (en) | 2017-01-19 | 2017-01-19 | A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106748613A true CN106748613A (en) | 2017-05-31 |
CN106748613B CN106748613B (en) | 2019-10-22 |
Family
ID=58944796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710040319.0A Active CN106748613B (en) | 2017-01-19 | 2017-01-19 | A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106748613B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109833906A (en) * | 2017-11-24 | 2019-06-04 | 中国石油天然气股份有限公司 | Bifunctional catalyst for preparing low-condensation-point biodiesel and preparation method and application thereof |
CN110304984A (en) * | 2019-08-13 | 2019-10-08 | 黑龙江大学 | A method of isohexadecane is produced using efficient bifunctional catalyst |
CN114956942A (en) * | 2022-06-01 | 2022-08-30 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexadecane |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001023501A1 (en) * | 1999-09-30 | 2001-04-05 | Virginia Tech Intellectual Properties, Inc. | Novel transition metal phosphide catalysts |
CN102887809A (en) * | 2012-10-17 | 2013-01-23 | 天津大学 | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst |
-
2017
- 2017-01-19 CN CN201710040319.0A patent/CN106748613B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001023501A1 (en) * | 1999-09-30 | 2001-04-05 | Virginia Tech Intellectual Properties, Inc. | Novel transition metal phosphide catalysts |
CN102887809A (en) * | 2012-10-17 | 2013-01-23 | 天津大学 | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst |
Non-Patent Citations (1)
Title |
---|
张建伟等: "《第18届全国分子筛学术大会论文集(上)》", 9 January 2017 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109833906A (en) * | 2017-11-24 | 2019-06-04 | 中国石油天然气股份有限公司 | Bifunctional catalyst for preparing low-condensation-point biodiesel and preparation method and application thereof |
CN109833906B (en) * | 2017-11-24 | 2021-11-30 | 中国石油天然气股份有限公司 | Bifunctional catalyst for preparing low-condensation-point biodiesel and preparation method and application thereof |
CN110304984A (en) * | 2019-08-13 | 2019-10-08 | 黑龙江大学 | A method of isohexadecane is produced using efficient bifunctional catalyst |
CN110304984B (en) * | 2019-08-13 | 2022-03-15 | 黑龙江大学 | Method for preparing isohexadecane by using bifunctional catalyst |
CN114956942A (en) * | 2022-06-01 | 2022-08-30 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexadecane |
CN114956942B (en) * | 2022-06-01 | 2023-12-22 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexadecane |
Also Published As
Publication number | Publication date |
---|---|
CN106748613B (en) | 2019-10-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2821753C (en) | Catalysts, methods of preparation of catalyst, methods of deoxygenation, and systems for fuel production | |
CN106748613B (en) | A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel | |
JP2017521232A (en) | Catalyst suitable for production of aircraft kerosene from synthetic oil obtained by biomass Fischer-Tropsch process and process for its preparation | |
Xiao et al. | Hydrodeoxygenation of fatty acid methyl esters and simultaneous products isomerization over bimetallic Ni‐Co/SAPO‐11 catalysts | |
Wang et al. | Anchoring Co on CeO2 nanoflower as an efficient catalyst for hydrogenolysis of 5-hydroxymethylfurfural | |
Cheng et al. | Ni-based metal–organic frameworks prepared with terephthalic acid hydroxylation converted methyl palmitate into jet-fuel range hydrocarbons in CO2 atmosphere | |
CN104923233A (en) | Core-shell structured catalyst for preparation of cyclohexanol by selective hydrodeoxygenation of catalytic guaiacol | |
Lin et al. | NiCo/SiO2 nanospheres for efficient synergetic decarboxylation of fatty acids and upgrading of municipal sludge HTL bio-crude to biofuels | |
CN110304984A (en) | A method of isohexadecane is produced using efficient bifunctional catalyst | |
CN106807439A (en) | A kind of cobalt-base catalyst and preparation method thereof | |
Lin et al. | Hierarchical porous honeycomb NiCo/C catalyst for decarboxylation of fatty acids and upgrading of sludge bio-crude | |
CN103785406A (en) | Transition metal composite oxide integral type hydrodeoxygenation catalyst and preparation method thereof | |
Wu et al. | Synthesis of Ni/SAPO-11-X zeolites with graded secondary pore structure and its catalytic performance for hydrodeoxygenation-isomerization of FAME for green diesel production | |
EP2422875A1 (en) | Method of manufacturing a catalyst and method for preparing fuel from renewable sources using the catalyst | |
CN106635118B (en) | A kind of method that waste oil directly prepares positive isoparaffin | |
Chen et al. | Synergistic effects of surface acidity and alkalinity of Ni/γ-Al2O3 catalysts in fats and oils hydrodeoxygenation product distribution | |
Habibie et al. | Effect of NiMo/zeolite catalyst preparation method for bio jet fuel synthesis | |
CN117414840A (en) | Method for preparing supported Ni-MoOx catalyst by adopting dielectric barrier discharge plasma and application thereof | |
CN109806908A (en) | A kind of catalyst of Biomass Syngas preparing liquid fuel and its preparation and application | |
Yu et al. | Co catalysts on various supports for lipid hydrotreatment to produce green diesel | |
RU2652990C1 (en) | Catalyst and method for producing transport fuel components of hydrocarbon composition using such catalyst | |
Wu et al. | In-situ preparation of MnFeCoNiCu/C for the sustainable co-production of bio-jet fuel and green diesel under solvent-free and low hydrogen pressure conditions | |
CN116943649A (en) | Preparation method and application of Pt/AlSiO-Nb hydrodeoxygenation coupling isomerization catalyst | |
Chu et al. | Hydrogen Storage by Liquid Hydrogen Carriers: Catalyst, Renewable Carrier, and Technology-A Review | |
CN111085242A (en) | Method and catalyst for preparing hydrogen by catalyzing methane with microwaves |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |