CN104549468B - Hydrocracking catalyst and preparation method - Google Patents
Hydrocracking catalyst and preparation method Download PDFInfo
- Publication number
- CN104549468B CN104549468B CN201310512285.2A CN201310512285A CN104549468B CN 104549468 B CN104549468 B CN 104549468B CN 201310512285 A CN201310512285 A CN 201310512285A CN 104549468 B CN104549468 B CN 104549468B
- Authority
- CN
- China
- Prior art keywords
- zsm
- catalyst
- hours
- grams
- hydrocracking
- 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.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a kind of catalyst of hydrocracking and preparation method thereof, mainly solve existing catalyst when for petroleum hydrocarbon hydrocracking steamcracker feed process, there is technical issues that low hydrogenation cracking activity and ethane and propane selectivity.The present invention by weight percentage, includes following components by using catalyst：a）0.1 ~ 2.0% selected from least one of Pd or Pt metals；b）98 ~ 99.9% technical solutions selected from least one of soap-free emulsion polymeization dosage form ZSM 5 and 23 cocrystallization composite molecular screen of ZSM 22 or ZSM, preferably resolve the problem, in the industrial production available for petroleum hydrocarbon hydrocracking steamcracker feed.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method, particularly to be carbon number to be pure between 4 to 15
Hydrocarbon or various hydrocarbon mixtures pass through hydrocracking processes ethane and the catalyst of propane for raw material.
Background technology
Ethylene and propylene are most important two kinds of basic organic chemical industry raw materials.At present, the main producer of ethylene and propylene
Formula is still by way of steam cracking.Currently, a large amount of industrial data confirms, with the change weight of cracking stock, cracks product
In ethylene and propylene yield present downward trend.By taking ethane as an example, under the reaction temperature more than 850 DEG C, ethylene
Yield is up to more than 75%.And propane, under similar cracking temperature, the yield of ethylene+propylene is up to 60%.And it is current, with routine
Naphtha is raw material, and the yield of ethylene+propylene is substantially 50% or so.Therefore, using ethane and propane as cracking stock, from production
From the point of view of in terms of the consumption of raw materials of ethylene and propylene, than the cracking stock of heavy --- naphtha is advantageously.At present, with North America
The exploitation of shale gas, light hydrocarbon product cracking can come the industrial zone of existing leading cracking naphtha production ethylene and propylene powerful
Impact.
Patent WO2012/071137A1 is reported using ZSM-5, ZSM-22, ZSM-11, ZSM-48, ZSM-23, ITQ-
The metallic element of zeolite-loaded 8th races of 13 and FER is catalyst, is 3 ~ 100bar in 200 ~ 650 DEG C of reaction temperature, pressure
Reaction condition under, method that the hydrocarbon raw material of C4 ~ C12 is converted into ethane and propane.
Be presently used for fixed bed catalyst molecular sieve catalyst composition in, will introduce greatly aluminium oxide, silica and
The silicon such as amorphous silica-alumina, aluminum oxide material make catalyst have preferable mechanical strength and shape as binding agent.Catalyst
Middle introducing binding agent can not only reduce the content of catalytic active component-molecular sieve, the adsorbance of catalyst be caused to decline, effectively
Surface area reduces.And since binding agent can enter zeolite cavity or blocking portion zeolite aperture, so as to cause reactant and production
Diffusion hindered, the adsorption capacity of object weaken, and so as to which the activity for causing catalyst reduces, induce secondary side reaction, lead to product
Selectivity reduce.The binder component that tradition molding introduces completely or partially such as is converted into zeolite, fluidisation can be effectively improved
The content of active component-zeolite in catalyst improves its effective active specific surface, mitigates the stopping state in reaction duct, can
It can improve the activity and selectivity of catalyst.It is compareed with catalyst of the routine containing binding agent, this Zeolite molecular sieve catalysis
Agent is referred to as catalyst based on binder-free zeolite molecular sieves.
At present, the existing molecular sieve catalyst containing binding agent, the weight content of its general binding agent is 15% to 30 or so,
Binder component can be SiO2Or aluminium oxide.
In conclusion when the prior art is applied to hydrocarbons hydrogenation cracking steam crack material processed, due to existing molecular screen base
In catalyst composition, contain binding agent（For example, aluminium oxide or silica）Component can reduce containing for active principle-molecular sieve
Amount, blocks the duct of molecular sieve, adsorbance is caused to decline, reduce the effective surface area of molecular sieve, therefore its cracking is caused to live
Property low and ethane and propane selectivity it is poor the technical issues of.
Invention content
The first technical problem to be solved by the present invention is that existing catalyst is applied to catalytic pyrolysis steamcracker feed
During process, there is low lytic activity and ethane and propane selectivity.The present invention proposes a kind of new plus hydrogen
Catalyst for cracking, this method crack steamcracker feed process processed for hydrocarbons hydrogenation, have lytic activity height and ethane and third
The advantages of alkane high selectivity.
The second technical problem to be solved by the present invention is to provide a kind of one of to solve the problems, such as corresponding catalyst
Preparation method.
The third technical problem to be solved by the present invention is to provide a kind of one of to solve the problems, such as corresponding catalyst
Purposes.
One of to solve above-mentioned technical problem, the technical solution adopted in the present invention is as follows：A kind of hydrocracking production is light
Matter catalyst for cracking bed, catalyst by weight percentage, include following components：a）0.1 ~ 2.0% in Pd or Pt metals
At least one；b）98.0 ~ 99.9% selected from soap-free emulsion polymeization dosage form ZSM-5 and ZSM-22 composite molecular screen carrier or ZSM-5 and
At least one of ZSM-23 composite molecular screen carriers.
In above-mentioned technical proposal, preferred technical solution is, wherein by weight percentage, the Pt that is loaded on catalyst or
The dosage of person Pd is preferably 0.4 ~ 0.8%；SiO in ZSM-5 molecular sieve2With Al2O3Molar ratio is 20 ~ 300；Binder free carries
The relative crystallinity of ZSM-5 in body is 9 ~ 88%.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：The hydrocracking catalyst
Preparation method, include the following steps：
I）It is 100 parts of SiO according to weight composition2：0. 57 ~ 3.4 parts of Al2O3：0 ~ 16.5 part of M2O：0 ~ 300 part of crystal seed：10~
900 parts of ZSM-5, by making for the hydroxide of the desired amount of alkali metal, silicon source, silicon source, crystal seed, ZSM-5 and solid amount 1 ~ 10%
Hole agent is uniformly mixed, and adds in the water of solid amount 0 ~ 120% with extruded moulding after mixing, at 80 ~ 250 DEG C dry 2 ~ 24
Hour obtained crystallization precursor WS1；
II）It is 100WS1 according to weight composition：10 ~ 200 templates：0~100H2O weighs the desired amount of template, water
Be placed in closed container bottom, weigh the desired amount of crystallization precursor and be placed in and be isolated on pallet with closed container bottom, not with
Liquid is in direct contact, and in confined conditions, crystallization 12 ~ 180 hours at 120 ~ 180 DEG C are washed, dry at 100 ~ 140 DEG C
ZSM-5 and ZSM-22 the composite molecular screen carrier for obtaining soap-free emulsion polymeization dosage form in 1 ~ 12 hour are roasted at dry 2 ~ 24 hours, 500 ~ 750 DEG C
Or ZSM-5 and ZSM-23 composite molecular screen carriers NWS1；
III）It is 2 ~ 24 hours dry at 100 ~ 140 DEG C by NWS1 at 50 ~ 90 lower DEG C after ammonium ion exchanges three times, 500
It is roasted at ~ 750 DEG C and obtains within 1 ~ 12 hour Hydrogen binder free carrier HWS1；
IV）The desired amount of preceding body for being selected from least one of Pd or Pt metals is loaded on HWS1 using infusion process
Body roasts 1 ~ 12 hour at 2 ~ 24 hours, 500 ~ 750 DEG C dry at 100 ~ 140 DEG C, obtains soap-free emulsion polymeization dosage form Aromatizatian catalytic
Agent.
In above-mentioned technical proposal, preferred technical solution is that template used dose of ZSM-22 is selected from ethylenediamine, Putriscine
Amine and 1,6 hexamethylene diamines, template used dose of ZSM-23 is in pyrrolidines, isopropylamine, n,N-Dimethylformamide or dimethylamine
At least one；Silicon source is selected from least one of white carbon, Ludox, diatomite, sodium metasilicate and waterglass, silicon source choosing
From at least one of aluminum sulfate, aluminum nitrate, sodium aluminate or aluminium chloride.The precursor of Pt elements is from chloroplatinic acid, Pt (NH3)4·
Cl2, the precursor of Pd elements is from palladium bichloride, Pd (NH3)4·Cl2。
To solve above-mentioned technical problem three, the technical solution adopted by the present invention is as follows：A kind of hydrocracking produces lightweight
The method of steam crack material, hydrocarbon raw material is in 260 ~ 520 DEG C, 0.1 ~ 10MPa of reaction pressure of reaction temperature, raw material weight air speed
0.1 ~ 6 hour-1Under conditions of, raw material is in contact with above-mentioned catalyst, obtains the effluent containing ethane and propane.
In above-mentioned technical proposal, preferred technical solution is that hydrocarbon raw material is any one group between carbon number is 4 to 16
Point or several hydro carbons mixture；Preferably ranging from 230 ~ 450 DEG C of reaction temperature, reaction pressure preferably ranging from 1.0 ~
6MPa, the preferred range of raw material weight air speed 0.3 ~ 2.0 hour-1。
Zeolite support cited in conventional catalyst catalyst for cracking is often required to the binder component introduced, so not only can
Cause the content of molecular sieve and reduce, catalytic activity reduces, and binding agent can also blocking portion zeolite aperture, so as to cause reaction
The diffusion hindered of object and product, secondary side reaction increase, and lead to the cracking of product selectively to reduce.Using it is of the present invention not
ZSM-5 containing binding agent and ZSM-22 or ZSM-23 molecular screen carrier, can not only effectively improve active component in catalyst-
The content of zeolite so as to which catalyst hydrogenation lytic activity be enable to be promoted, and can mitigate the stopping state in reaction duct, improve
The selectivity of catalyst ethane and propane.
The present invention is added using ZSM-5 and ZSM-22 or the ZSM-23 composite molecular screen without binding agent as prepared by carrier
Hydrogen catalyst for cracking under identical reaction conditions, is cracked using catalyst prepared by the present invention for hydrocracking lightweight
In raw material reaction, the hydrocracking activity of catalyst is higher 4-7% than existing catalyst, and the selectivity of ethane and propane is urged than existing
The high 5-7% of agent, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.But these embodiments are not to the scope of the present invention
It is limited.
Specific embodiment
The relative crystallinity of ZSM-5 zeolite is calculated using commercial ZSM-5 zeolite in synthetic sample（SiO2With Al2O3Mole
Than being 50, Nankai's catalyst plant）On the basis of, sample is in the XRD angles of diffraction 5 ~ 40oThe peak area of XRD diffraction maximums and the peak of standard specimen
The ratio of area is the relative crystallinity of ZSM-5 in the sample.
【Embodiment 1】
Weigh 202 grams of white carbons（99%SiO2）, 8.35 grams of aluminum nitrate, 3.33 grams of sodium hydroxides, 60 grams of sesbania powders, 1800
Gram ZSM-5（The molar ratio of silica and aluminium oxide is 400）And 2400 grams of water extruded moulding after mixing, it is dry at 250 DEG C
Dry 24 hours obtained crystallization precursor WS1.
10 grams of ethylenediamines and 50 grams of water are weighed as reactor bottom, 100 grams of crystallization precursors is weighed and is placed in and template
On the trepanning bracket of isolation, crystallization 12 hours at 180 DEG C.Crystallization product be washed with deionized three times, it is dry at 140 DEG C
It is roasted 12 hours at 2 hours, 500 DEG C and obtains soap-free emulsion polymeization carrier NWS1.
By NWS1 in 80 lower DEG C, solid-to-liquid ratio 1:10th, under conditions of 1 mole of ammonium nitrate solution rises, three are exchanged through ammonium ion
After secondary, roasted at 4 hours, 650 DEG C dry at 140 DEG C and obtain within 3 hours Hydrogen binder free carrier HWS1, wherein ZSM-5's
Relative crystallinity is 88%.
Take 49 grams of HWS1,45 grams of dipping containing gram aqueous solution.It is aged at room temperature 8 hours, then drying 12 is small at 120 DEG C
When, it is roasted 4 hours at 550 DEG C and obtains catalyst a.
49.5 grams of HWS1 are taken, 45 grams of dipping contains 0.856 gram of Pt (NH3)4·Cl2Aqueous solution.Ageing 8 hours at room temperature, so
It is 12 hours dry at 120 DEG C afterwards, it is roasted 4 hours at 550 DEG C and obtains catalyst a.
The composition of catalyst is listed in table 1 with weight percent.The catalyst of all embodiments and comparative example is using simultaneously
Method is checked and rated, and examination condition is：320 DEG C, 100% normal heptane, the molar ratio of hydrogen and normal heptane is 4.0, the weight of normal heptane
Air speed is 2.0 hours-1, normal pressure, reaction result is listed in table 2.
【Embodiment 2】
Weigh 450 grams of Ludox（40%SiO2）, 31.2 grams of aluminium chloride, 39.3 grams of potassium hydroxide, 15 grams of polyethylene glycol（Point
Son amount is 8000）And 20 grams of ZSM-5 crystal seeds（The molar ratio of silica and aluminium oxide is 50）Extruded moulding after mixing,
80 DEG C of dryings, 2 hours obtained crystallization precursor WS2.
It weighs 100 grams of Putriscines and is placed in reactor bottom, weigh 100 grams of crystallization precursor WS2 and be placed in and reaction kettle
On the trepanning bracket of the polytetrafluoroethylene (PTFE) of bottom isolation, crystallization 180 hours at 180 DEG C.Crystallization product is washed with deionized
Three times, the opposite knot for obtaining soap-free emulsion polymeization carrier NWS2, wherein ZSM-5 for 12 hours is roasted at drying 2 hours, 500 DEG C at 140 DEG C
Brilliant degree is 9%.
By NWS2 in 80 lower DEG C, solid-to-liquid ratio 1:10th, under conditions of 1 mole of ammonium nitrate solution rises, three are exchanged through ammonium ion
After secondary, roasted at 8 hours, 550 DEG C dry at 120 DEG C and obtain within 6 hours Hydrogen binder free carrier HWS2.
49.7 grams of HWS2 are taken, 46.0 grams of dipping contains 0.257 gram of Pt (NH3)4·Cl2With 0.346 gram of Pd (NH3)4·Cl2Water
Solution, after being aged 8 hours at room temperature, at 120 DEG C dry 12h, roasting 4h obtains catalyst b, the evaluation of catalyst at 550 DEG C
Method is the same as embodiment 1.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
【Embodiment 3】
Weigh 250 grams of Ludox（40%SiO2）, 22.22 grams of aluminum sulfate, 9.0 grams of potassium hydroxide, 12 grams of polyvinyl alcohol（Point
Son amount is 8000）, 300 grams of ZSM-22 zeolites, 133.7 grams of ZSM-5 zeolites（The molar ratio of silica and aluminium oxide is 100）And
517 grams of water extruded moulding after mixing, in 120 DEG C of dry 12 hours obtained crystallization precursor WS3.
20 grams of 1,6- hexylamines and 40 grams of water are weighed as reactor bottom, 100 grams of crystallization precursors is weighed and is placed in polytetrafluoro
On the trepanning bracket of ethylene, crystallization 72 hours at 160 DEG C.Crystallization product be washed with deionized three times, it is dry at 140 DEG C
It is roasted 2 hours at 2 hours, 700 DEG C and obtains soap-free emulsion polymeization carrier NWS3.
By NWS3 in 80 lower DEG C, solid-to-liquid ratio 1:10th, under conditions of 1 mole of ammonium nitrate solution rises, three are exchanged through ammonium ion
After secondary, roasted 1 ~ 12 hour at 2 ~ 24 hours, 500 ~ 750 DEG C dry at 100 ~ 140 DEG C and obtain Hydrogen binder free carrier
The relative crystallinity of HWS3, ZSM-5 are 25.2%.
Take 49.0 grams of HWS3,45.0 grams of aqueous solutions for containing gram 2.65 grams of chloroplatinic acids of dipping.Ageing 8 hours at room temperature, then
The dry 12h at 120 DEG C, roasting 4h obtains catalyst c at 550 DEG C, and the evaluation method of catalyst is the same as embodiment 1.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
【Embodiment 4】
Weigh 384 grams of waterglass（8.2%Na2O, 26.0%SiO2）, 101.2 grams of white carbons, 2.73 grams of sodium aluminates, 12 grams it is poly-
Acrylamide（Molecular weight is 20000）, 196.8 grams of ZSM-5 molecular sieves（The molar ratio of silica and aluminium oxide is 240）And
120 grams of water extruded moulding after mixing, in 250 DEG C of dry 24 hours obtained crystallization precursor WS4.
20 grams of pyrrolidines and 50 grams of water are weighed as reactor bottom, 100 grams of crystallization precursors is weighed and is placed in and water, template
On the trepanning bracket of the polytetrafluoroethylene (PTFE) of agent isolation, crystallization 120 hours at 120 DEG C.Crystallization product is washed with deionized three
It is roasted 12 hours at secondary, 2 hours, 500 DEG C dry at 140 DEG C and obtains soap-free emulsion polymeization carrier NWS4.
By NWS4 in 80 lower DEG C, solid-to-liquid ratio 1:10th, under conditions of 1 mole of ammonium nitrate solution rises, three are exchanged through ammonium ion
After secondary, roasted at 4 hours, 650 DEG C dry at 140 DEG C and obtain within 2 hours the opposite of Hydrogen binder free carrier HWS4, ZSM-5
Crystallinity is 49.2%.
Take 48 grams of HWS4, aqueous solution of 46.2 grams of the dipping containing 1.70 yttrium nitrates and 0.083 gram of palladium bichloride.It is aged 8 at room temperature
12h is dried after hour at 120 DEG C, 4h is roasted at 550 DEG C and obtains catalyst d, the evaluation method of catalyst is the same as embodiment 1.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
【Embodiment 5】
Weigh 202 grams of white carbons（40%SiO2）, 10.43 grams of aluminum nitrate, 9.2 grams of potassium hydroxide, 131.1 grams of ZSM-5 molecules
Sieve（The molar ratio of silica and aluminium oxide is 240）And 280 grams of water extruded moulding after mixing, it is 4 hours dry at 120 DEG C
Crystallization precursor WS5 is made.
Weigh 100 grams of isopropylamines and be placed in reactor bottom, 100 grams of crystallization precursors be placed in be isolated with water template it is poly-
On the trepanning bracket of tetrafluoroethene, crystallization 180 hours at 120 DEG C.Crystallization product is washed with deionized three times, at 140 DEG C
It is roasted 12 hours at lower drying 2 hours, 500 DEG C and obtains binder free carrier NWS5.
By NWS5 in 80 lower DEG C, solid-to-liquid ratio 1:10th, under conditions of 1 mole of ammonium nitrate solution rises, three are exchanged through ammonium ion
After secondary, roasted 2 hours at 12 hours, 750 DEG C dry at 120 DEG C and obtain the phase of Hydrogen binder free carrier HWS5, ZSM-5
It is 39.6% to crystallinity.
Catalyst e is obtained according to the identical preparation method of embodiment 1, the evaluation method of catalyst is the same as embodiment 1.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
【Embodiment 6】
Weigh 250 grams of Ludox（40%SiO2）, 5.36 grams of aluminium chloride, 11.2 grams of sodium hydroxides and 80 grams of ZSM-5（Oxygen
SiClx and the molar ratio of aluminium oxide are 150）Extruded moulding after mixing, in 120 DEG C of dry 8 hours obtained crystallization precursors
WS6。
It weighs 70 grams of n,N-Dimethylformamide and is placed in reactor bottom, 100 grams of crystallization precursors are with being placed in and water template
On the trepanning bracket of the polytetrafluoroethylene (PTFE) of agent isolation, crystallization 180 hours at 120 DEG C.Crystallization product is washed with deionized three
It is roasted 12 hours at secondary, 2 hours, 500 DEG C dry at 140 DEG C and obtains the relative crystallinity of binder free carrier NWS6, ZSM-5
It is 28.0%.
By NWS5 in 80 lower DEG C, solid-to-liquid ratio 1:10th, under conditions of 1 mole of ammonium nitrate solution rises, three are exchanged through ammonium ion
After secondary, roasted at 24 hours, 500 DEG C dry at 100 DEG C and obtain within 12 hours Hydrogen binder free carrier HWS6.
Catalyst f is obtained according to the identical preparation method of embodiment 1, the evaluation method of catalyst is the same as embodiment 1.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
【Embodiment 7】
Weigh 250 grams of Ludox（40%SiO2）, 5.36 grams of aluminium chloride, 11.2 grams of sodium hydroxides and 80 grams of ZSM-5（Oxygen
SiClx and the molar ratio of aluminium oxide are 150）Extruded moulding after mixing, in 120 DEG C of dry 8 hours obtained crystallization precursors
WS7。
Weigh 50 grams of dimethylamine and be placed in reactor bottom, 100 grams of crystallization precursors be placed in be isolated with water template it is poly-
On the trepanning bracket of tetrafluoroethene, crystallization 180 hours at 120 DEG C.Crystallization product is washed with deionized three times, at 140 DEG C
It is roasted 12 hours at lower drying 2 hours, 500 DEG C and obtains binder free carrier NWS7.
By NWS5 in 80 lower DEG C, solid-to-liquid ratio 1:10th, under conditions of 1 mole of ammonium nitrate solution rises, three are exchanged through ammonium ion
After secondary, roasted at 4 hours, 550 DEG C dry at 140 DEG C and obtain within 6 hours the opposite of Hydrogen binder free carrier HWS7, ZSM-5
Crystallinity is 28.6%.
Catalyst g is obtained according to the identical preparation method of embodiment 1, the evaluation method of catalyst is the same as embodiment 1.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
At present, the existing molecular sieve catalyst containing binding agent, the weight content of its general binding agent is 15% to 30 or so,
Binder component can be SiO2Or aluminium oxide.
【Comparative example 1】
The alumina bound agent content of catalyst is that the content of 20%, ZSM-5 is identical with the HWS3 in embodiment 3, remaining is
ZSM-22（The molar ratio of silica and aluminium oxide is 100, identical with silica alumina ratio in WS3 in embodiment 3）.Take 50.4 grams of ZSM-5
（The molar ratio of silica and aluminium oxide is 100）, 105.6 grams of ZSM-22（The molar ratio of silica and aluminium oxide is 100）, 6 grams
Sesbania powder and 57.1 grams of aluminium oxide（70%Al2O3）Through kneading, extruded moulding, roasted at 8 hours, 550 DEG C dry at 120 DEG C
Obtain carrier HYN1 within 6 hours.The content of dip composition is same as Example 2, and the preparation method of catalyst is according to 1 side of embodiment
Prepared by method, catalyst is denoted as x.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
【Comparative example 2】
The silica bound agent content of catalyst is that the content of 20%, ZSM-5 is identical with the HWS4 in embodiment 4, remaining is
ZSM-22（The molar ratio of silica and aluminium oxide is the molar ratio phase of silica and aluminium oxide in WS4 in 240, with embodiment 4
Together）.Take 50.4 grams of ZSM-5（The molar ratio 240 of silica and aluminium oxide）, 105.6 grams of ZSM-22,6 grams of sesbania powders and 57.1
Gram aluminium oxide（70%Al2O3）Through kneading, extruded moulding, roasted 6 hours at 8 hours, 550 DEG C dry at 120 DEG C and obtain carrier
HYN2 。
The content of dip composition is same as Example 4, and the preparation method of catalyst is prepared according to 4 method of embodiment, catalysis
Agent is denoted as y.
The composition of catalyst is shown in Table 1 with weight percent, and reaction result is shown in Table 2.
【Embodiment 8 ~ 13】
Embodiment 8 ~ 13 is the reaction result obtained using catalyst b, change technological parameter with reaction raw materials, catalyst
Appraisal result can be shown in Table 3.
It is compared by embodiment in table 23,4 and Comparative Examples 1 and 2 and table 3 is it can be found that under identical reaction conditions, adopt
The reaction of hydrocarbon catalytic cracking steamcracker feed, the hydrocracking activity of catalyst are used for catalyst prepared by the present invention
Higher 4-7% than existing catalyst, the selectivity of ethane and propane is higher 5-7% than existing catalyst, achieves preferable technology effect
Fruit.
Table 1
Table 2
| Embodiment | Catalyst | Conversion ratio/% of normal heptane | Ethane+propane selectivity/% |
| 1 | a | 48.2 | 56.7 |
| 2 | b | 65.3 | 75.6 |
| 3 | c | 63.7 | 73.5 |
| 4 | d | 58.3 | 62.5 |
| 5 | e | 57.2 | 70.5 |
| 6 | f | 62.9 | 74.8 |
| 7 | g | 63.5 | 74.3 |
| Comparative example 1 | x | 56.2 | 67.5 |
| Comparative example 2 | y | 53.7 | 57.4 |
Table 3
Claims (9)
1. a kind of hydrocracking catalyst in terms of catalyst weight percent, includes following components：
A) 0.1~2.0% selected from least one of Pd or Pt metals；
B) 98.0~99.9% ZSM-5 and ZSM-22 the composite molecular screen carrier of soap-free emulsion polymeization dosage form or ZSM-5 and ZSM-23 are selected from
At least one of composite molecular screen carrier；
The preparation method of the hydrocracking catalyst, includes the following steps：
I it is) 100 parts of SiO according to weight composition2：0.43~3.4 part of Al2O3：0~16.5 part of alkali metal M2O：0~300 part of crystal seed：
10~900 parts of ZSM-5, and alkali metal M2The parts by weight of O do not include 0, by the desired amount of alkali metal M2The hydroxide of O, silicon source,
Silicon source, crystal seed, ZSM-5 and solid amount 1~10% pore creating material be uniformly mixed, and add in the water of solid amount 0~120% with
After mixing, extruded moulding, in 80~250 DEG C of dry 2~24 hours obtained crystallization precursor WS1；
II it is) 100WS1 according to weight composition：10~200 templates：0~100H2O weighs the desired amount of template, water is placed in
Closed container bottom weighs the desired amount of crystallization precursor and is placed on the pallet being isolated with closed container bottom, not with liquid
It is in direct contact, in confined conditions, crystallization 12~180 hours at 120~180 DEG C are washed, dry at 100~140 DEG C
It is compound that 1~12 hour ZSM-5 and ZSM-22 for obtaining soap-free emulsion polymeization dosage form or ZSM-23 is roasted at 2~24 hours, 500~750 DEG C
Molecular sieve carrier NWS1；
III) by NWS1 at 50~90 DEG C after ammonium ion exchanges three times, dry 2~24 hours at 100~140 DEG C, 500
It is roasted at~750 DEG C and obtains within 1~12 hour Hydrogen binder free carrier HWS1；
IV the desired amount of precursor for being selected from least one of Pd or Pt metals) is loaded on HWS1 using infusion process,
It is roasted 1~12 hour at drying 2~24 hours, 500~750 DEG C at 100~140 DEG C and obtains soap-free emulsion polymeization dosage form Aromatizatian catalytic
Agent.
2. hydrocracking catalyst according to claim 1, it is characterised in that in terms of catalyst weight percent, Pt or
The dosage of Pd is 0.4~0.8%.
3. hydrocracking catalyst according to claim 1, it is characterised in that ZSM-5 molecular sieve in composite molecular screen carrier
In SiO2With Al2O3Molar ratio is 20~400.
4. hydrocracking catalyst according to claim 1, it is characterised in that ZSM-5's in binder free carrier is opposite
Crystallinity is 9~88%.
5. hydrocracking catalyst according to claim 1, it is characterised in that step I) in M metals be selected from Na or K
At least one of element.
6. hydrocracking catalyst according to claim 1, it is characterised in that template used dose of ZSM-22 molecular sieves are selected from
Ethylenediamine, butanediamine and 1,6- hexamethylene diamine, template used dose of ZSM-23 molecular screen is selected from pyrrolidines, isopropylamine, N, N- diformazans
At least one of base formamide or dimethylamine.
7. hydrocracking catalyst according to claim 1, it is characterised in that silicon source is selected from white carbon, Ludox, diatom
At least one of soil and waterglass, silicon source are selected from least one of aluminum sulfate, aluminum nitrate, sodium aluminate or aluminium chloride；It is brilliant
Kind is ZSM-22 or ZSM-23 molecular screen；Pore creating material is sesbania powder, in polyethylene glycol, polyvinyl alcohol, polyacrylamide, starch
It is at least one.
8. a kind of method of hydrocracking production carbon dioxide cracking stock, hydrocarbon raw material is 260~520 DEG C in reaction temperature,
Reaction pressure is 0.1~10MPa, and raw material weight air speed is 0.1~6 hour-1Under conditions of, raw material in claim 1~7 with appointing
A kind of catalyst of anticipating contacts, and obtains the effluent containing ethane and propane.
9. the method for hydrocracking production carbon dioxide cracking stock according to claim 8, it is characterised in that hydro carbons is former
Expect for carbon number be 4 to 16 between any one component or several hydro carbons mixture, reaction temperature be 230~450 DEG C, reaction
Pressure is 1.0~6MPa, and raw material weight air speed is 0.3~2.0 hour-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512285.2A CN104549468B (en) | 2013-10-28 | 2013-10-28 | Hydrocracking catalyst and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512285.2A CN104549468B (en) | 2013-10-28 | 2013-10-28 | Hydrocracking catalyst and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549468A CN104549468A (en) | 2015-04-29 |
| CN104549468B true CN104549468B (en) | 2018-06-08 |
Family
ID=53067171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310512285.2A Active CN104549468B (en) | 2013-10-28 | 2013-10-28 | Hydrocracking catalyst and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549468B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3028438C (en) * | 2016-06-24 | 2023-12-05 | Albemarle Corporation | Mesoporous zsm-22 for increased propylene production |
| CN106807442A (en) * | 2017-01-16 | 2017-06-09 | 惠生工程（中国）有限公司 | A kind of shape-selective catalyst with toluene methylation efficiency high and its preparation method and application |
| CN113385215B (en) * | 2021-06-11 | 2022-06-28 | 洛阳市科创石化科技开发有限公司 | Preparation method and application of catalyst for preparing propane by hydro-upgrading |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039162A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Binderless ZSM-5/beta zeolite symbiotic molecular sieve catalyst and preparation method thereof |
-
2013
- 2013-10-28 CN CN201310512285.2A patent/CN104549468B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039162A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Binderless ZSM-5/beta zeolite symbiotic molecular sieve catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549468A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9339801B2 (en) | Molded catalyst for the conversion of methanol to aromatics and process for producing the same | |
| CN106362791B (en) | One kind is for compound duct molecular sieve catalyst of the preparing propylene transformed mesoporous-micropore of dehydrogenating propane and preparation method thereof | |
| CN103842079A (en) | Use of a catalyst comprising a phosphorus modified zeolite in an alcohol dehydration process | |
| CN106745036A (en) | With the microporous mesoporous molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application | |
| CN104549468B (en) | Hydrocracking catalyst and preparation method | |
| CN110615444A (en) | Mordenite molecular sieve, and preparation method and application thereof | |
| CN104386706B (en) | With the method that zinc amine complex synthesizes CHA type molecular sieve for template | |
| CN104549448A (en) | Method for producing light steam cracking raw materials by catalytic cracking | |
| CN105983434B (en) | A kind of preparation method and application of the ZSM-11 molecular sieve catalyst of binder free | |
| CN106607079A (en) | Methanol-to-aromatic hydrocarbon catalyst and uses tehreof | |
| CN105645428B (en) | The preparation method of the molecular sieves of SSZ 32 with mesoporous micropore graded structure | |
| CN109046445B (en) | Preparation method of H beta/MCM-22 composite structure molecular sieve and method for preparing tert-butylphenol | |
| CN102039150B (en) | Preparation method of binderless Y zeolite catalyst | |
| CN104549456B (en) | Heavy aromatic lightening catalyst and preparation method thereof | |
| CN107867968B (en) | Method for reducing side reaction of hydrogenation ring opening of benzene ring | |
| CN107021504B (en) | A kind of preparation method of mesoporous IM-5 molecular sieve | |
| CN109529910B (en) | Catalyst for toluene methanol side-chain alkylation reaction and styrene preparation method | |
| CN101992122B (en) | Preparation method of binderless ZSM-5/beta zeolite symbiotic molecular sieve catalyst | |
| CN109569703B (en) | Catalyst for producing gasoline component from naphtha and methanol, preparation method and application | |
| KR20170127085A (en) | 3-dimensional mesoporous carbon catalysts for producing deoxygenated compounds from fatty acids | |
| CN1061269C (en) | Ni-B amorphous alloy catalyst, its preparing process and application | |
| CN103787367B (en) | Preparation method of binder-free ZSM-5 molecular sieve forming product | |
| CN112675902B (en) | Catalyst for preparing propylene by inverse disproportionation of ethylene and butene and preparation method thereof | |
| CN112619686B (en) | Supported non-noble metal dehydrogenation catalyst and preparation method and application thereof | |
| CN102039162B (en) | Binderless ZSM-5/beta zeolite symbiotic molecular sieve catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |