CN101108359A - Hydrocracking catalyst containing heteropolyacid and preparation method thereof - Google Patents
Hydrocracking catalyst containing heteropolyacid and preparation method thereof Download PDFInfo
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Abstract
含杂多酸的加氢裂化催化剂及其制备方法，涉及一种长链烷烃的加氢裂化催化剂及其制备方法。提供一种大孔径、高活性的含杂多酸的加氢裂化催化剂及其制备方法。包括杂多酸、加氢组分和载体，载体为多孔性耐热无机材料，加氢组分为双金属混合物，以催化剂重量为基准，催化剂各组分的含量中杂多酸为20％～70％，加氢组分镍与钴总含量以单质计为5％～20％，其中钴与镍的含量比为1/10～3/5，余量为载体。选择催化剂载体；配制加氢组分的金属盐水溶液；用金属盐水溶液浸渍载体，将液－固分离后的固体物烘干，焙烧；配制杂多酸水溶液；用杂多酸水溶液浸渍含镍和钴的固体物，静置，烘干，焙烧。A hydrocracking catalyst containing heteropolyacids and a preparation method thereof, relating to a hydrocracking catalyst of long-chain alkanes and a preparation method thereof. Provided are a large-pore size, high-activity heteropolyacid-containing hydrocracking catalyst and a preparation method thereof. It includes heteropolyacid, hydrogenation component and carrier. The carrier is a porous heat-resistant inorganic material. The hydrogenation component is a bimetallic mixture. Based on the weight of the catalyst, the content of heteropolyacid in each component of the catalyst is 20%~ 70%, the total content of nickel and cobalt in the hydrogenation component is 5% to 20% in terms of simple substances, wherein the content ratio of cobalt to nickel is 1/10 to 3/5, and the balance is carrier. Select the catalyst carrier; prepare the metal salt solution of the hydrogenation component; impregnate the carrier with the metal salt solution, dry and roast the solid after liquid-solid separation; prepare the heteropoly acid solution; impregnate the nickel and Cobalt solids, stand still, dry and roast.
Description
Technical field
The present invention relates to hydrocracking catalyst of a kind of long chain alkane and preparation method thereof, especially relate to a kind of hydrocracking catalyst that contains heteropoly acid and preparation method thereof.
Background technology
In petroleum refining industry, hydrocracking is the important process process of being produced the high-quality light-weight oil product by mink cell focus, and its technological core is a catalyst system therefor.Hydrocracking catalyst is a kind of bifunctional catalyst, has acid function and hydrogenating function concurrently.For example U.S. Pat 5,536, and 687 and US5,447,623; The acid function of the hydrocracking catalyst that European patent EP 0028938A1 etc. are involved mainly is to be provided by molecular sieve, and hydrogenation component is selected Mo-Ni or W-Ni for use.Chinese patent CN1389545A is involved contains Y zeolite 20%-40%, phosphorus heteropoly tungstic acid or silicotungstic heteropolyacid 5-20%, and nickel oxide 5-10%, the catalyst of aluminium oxide 40-60% all has These characteristics.
Contain molecular sieve hydrocracking catalyst and have acidity by force, the advantage that specific surface is big causes reactant and product diffusional resistance to increase but its shortcoming is a molecular sieve bore diameter for a short time, distributes for apparent reactivity and product and brings negative effect.
Summary of the invention
The object of the invention aims to provide a kind of large aperture, highly active hydrocracking catalyst that contains heteropoly acid and preparation method thereof.
The hydrocracking catalyst that contains heteropoly acid of the present invention comprises heteropoly acid, hydrogenation component and carrier, and carrier is the heat-resisting inorganic material of porous, and hydrogenation component is the bimetallic mixture, and heteropoly acid is H
3PW
12O
40NH
2O, H
3PMo
12O
40NH
2O, H
4SiW
12O
40NH
2O or H
4SiMo
12O
40NH
2O.With the catalyst weight is benchmark, and heteropoly acid is 20%～70% in each components contents of catalyst, and hydrogenation component nickel and cobalt total content count 5%～20% with simple substance, and wherein cobalt is 1/10～3/5 with the content ratio of nickel, and surplus is a carrier.
Carrier can be SiO
2Or aluminium oxide, carrier is preferably SiO
2The specific surface of carrier is more preferably greater than 300m
2.g
-1
The bimetallic mixture is the mixture of Ni and Co compound, is preferably nickel nitrate and cobalt nitrate mixed solution, nickel acetate and cobalt acetate mixed solution or nickel oxalate and cobalt oxalate mixed solution, preferred nickel nitrate of bimetallic mixture and cobalt nitrate mixed solution.
Heteropoly acid is preferably the H with Keggin structure
3PW
12O
40NH
2O or H
3PMo
12O
40NH
2O is especially with H
3PW
12O
40NH
2O is good.With the catalyst weight is benchmark, and heteropoly acid is preferably 40%～60% in each components contents of catalyst, and hydrogenation component nickel and cobalt total content are preferably 5%～10% in simple substance, and surplus is a carrier.
The preparation method who contains the hydrocracking catalyst of heteropoly acid of the present invention the steps include:
1) selecting catalyst carrier;
2) according to the aqueous metal salt of the constituent content of catalyst preparation hydrogenation component;
3) with the aqueous metal salt impregnated carrier 2～12h of step 2 preparation, the solids after the liquid-solid separation is dried 3～8h down at 80～150 ℃, again in 350～450 ℃ of following roasting 4～8h;
4) prepare the heteropoly acid aqueous solution according to the constituent content of catalyst;
5) with the heteropoly acid aqueous solution dipping of step 4 preparation solids, leave standstill 2～12h by the prepared nickeliferous and cobalt of step 3; At 80～150 ℃ of following oven dry 3～8h, again through 350～450 ℃ of roasting 4～8h, contain the hydrocracking catalyst of heteropoly acid.
Before using, the hydrocracking catalyst that contains heteropoly acid that the present invention is prepared carries out presulfurization.Its pre-vulcanization process is: with the CS of 5/95 (volume ratio)
2/ H
2As sulfiding gas, flow velocity 40～70mlmin
-1, vulcanize 3～8h down at 300～500 ℃.Then switch and feed hydrogen, reaction system progressively adherence pressure to the required pressure of hydrocracking reaction, promote the temperature of beds more gradually to the required temperature of hydrocracking reaction after hydrogen flowing quantity is stable, and hydrogen flowing quantity is adjusted to the required flow of hydrocracking reaction, progressively cut the reacted hydrocarbon raw material again after stable.
In the aforesaid operations process, hydrocracking reaction pressure, reaction temperature, hydrogen hydrocarbon volume ratio and hydrocarbon charging air speed are determined by hydrocarbon feed character, purpose product requirement and the catalyst performance of reaction.Usually, reaction pressure 1.0～10.0MPa, 270～400 ℃ of reaction temperatures, hydrogen hydrocarbon volume ratio 600～1800, hydrocarbon feed volume air speed 1.0～4.0h
-1
The hydrocracking catalyst that contains heteropoly acid of the present invention can be used for big molecule linear paraffin and contains for example hydrocracking and the hydroisomerizing reaction of various oil products of hydrocarbon mixture of big molecule linear paraffin.Hydrogenation cracking activity is represented by the conversion ratio of n-decane, and selectivity is designated as C by " the alkane molal quantity that contains 5 carbon atoms and 5 above carbon atoms in the product is divided by the product total mole number " expression
5+Selectivity.This is because in hydrocracking process, wishes more than pyrolysis product and the second pyrolysis product is few that when being the reacted hydrocarbon raw material with the n-decane, the alkane that contains 5 carbon atoms and 5 above carbon atoms in the product all is a pyrolysis product, so C
5+Selectivity has characterized the relative quantity of a pyrolysis product in the product.
The hydrocracking catalyst that contains heteropoly acid of the present invention is applied to hydrocracking reaction, and the gained conversion ratio reaches as high as more than 60%, and the selectivity of crackate is up to nearly 80%.This shows, adopt the prepared hydrocracking catalyst that contains heteropoly acid of the present invention under same reaction condition and close selective conditions, higher hydrogenation cracking activity to be arranged.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
(1) Preparation of Catalyst: getting 150ml concentration is 1molL
-1Nickel nitrate solution and 30ml concentration be 1molL
-1Cobalt nitrate solution be mixed with the mixed solution of nickel nitrate and cobalt nitrate, with the 60g specific surface greater than 300m
2.g
-1Carrier S iO
2Place mixed solution to leave standstill 12h, dry by the fire 5h down in 120 ℃ after the liquid-solid separation.With the oven dry after solids in muffle furnace with 6 ℃ of min
-1Speed rise to 400 ℃, constant temperature 5h.Baked catalyst soakage in containing the 70g phosphotungstic acid aqueous solution, is left standstill behind the 10h at 100 ℃ of dry 5h down, then at 430 ℃ of following roasting 4h.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.
(2) evaluation of catalyst: with the preparation catalyst at CS with 5/95 (volume ratio)
2/ H
2As vulcanizing 4h in 300 ℃ under the sulfiding gas.After sulfuration finishes, cut into hydrogen, stablize laggard n-decane at hydrogen flow rate.Hydrocracking conversion ratio and the product of evaluate catalysts under reaction condition distributes.Raw materials used and the reaction process condition of evaluation of catalyst activity sees Table 2, and the selectivity of gained conversion ratio and crackate sees Table 3.
Embodiment 2
In embodiment 1, changing the 70g phosphotungstic acid into the 98g phosphotungstic acid is the cost example.The chemical composition of catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 3
In embodiment 1, change the 70g phosphotungstic acid into the 28g phosphotungstic acid, i.e. the cost example.The chemical composition of catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 4
In embodiment 1, change the sintering temperature behind the load phosphotungstic acid into 380 ℃, i.e. the cost example.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 5
In embodiment 1, change the 70g phosphotungstic acid into the 70g phosphomolybdic acid, i.e. the cost example.The chemical composition of catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 6
In embodiment 1, change the 70g phosphotungstic acid into the 70g silico-tungstic acid, i.e. the cost example.The chemical composition of catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 7
In embodiment 1, change the 70g phosphotungstic acid into the 70g silicomolybdic acid, i.e. the cost example.The chemical composition of catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 8
In embodiment 1, with the 1molL of 150ml
-1Nickel nitrate solution change 300ml into, i.e. cost example.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 9
In embodiment 1, be 1molL with 150ml concentration
-1Nickel nitrate solution and 30ml concentration be 1molL
-1Cobalt nitrate solution change the nickel oxalate and the cobalt oxalate solution of equal-volume concentration, i.e. cost example into.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 10
(1) preliminary treatment of carrier: with the carrier specific surface is 300m
2G
-1Aluminium oxide standby behind 600 ℃ of roasting 4h.
(2) Preparation of Catalyst: it is 1molL that the alumina support that 60g is above-mentioned places 150ml concentration
-1Nickel nitrate solution and 30ml concentration be 1molL
-1Cobalt nitrate solution in, leave standstill 3h, then in 120 ℃ of following oven dry 5h.With the oven dry after solids in muffle furnace with 10 ℃ of min
-1Speed rise to 400 ℃, constant temperature 5h.Baked catalyst soakage in containing the 70g phosphotungstic acid aqueous solution, is left standstill behind the 10h at 100 ℃ of dry 5h down, then at 440 ℃ of following roasting 4h.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.
(3) evaluation of catalyst
With the catalyst of preparation at the CS of 5/95 (volume ratio)
2/ H
2As vulcanizing 4h in 300 ℃ under the sulfiding gas.After sulfuration finishes, cut into hydrogen, stablize laggard n-decane at hydrogen flow rate.Estimate hydrocracking conversion ratio and the product distribution (selectivity of gained conversion ratio and crackate see Table 3) of each catalyst under reaction condition.
Embodiment 11
In embodiment 1, be 1molL with 150ml concentration
-1Nickel nitrate solution change 540ml into, the 1molL of 30ml
-1Cobalt nitrate solution change the cobalt nitrate solution of 60ml, i.e. cost example into.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Embodiment 12
In embodiment 1, with the 1molL of 30ml
-1Cobalt nitrate solution change the cobalt nitrate solution of 90ml, i.e. cost example into.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Comparative example 1-5
Remove the aqueous solution that contains cobalt in the aqueous metal salt of the hydrogenation component among the embodiment 1～5 and be comparative example 1～5.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Comparative example 6
In embodiment 1, be 1molL with 150ml concentration
-1Nickel nitrate solution and 30ml concentration be 1molL
-1Cobalt nitrate solution change the 180ml nickel nitrate solution into, be this comparative example.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Comparative example 7
In embodiment 1, be 1molL with 150ml concentration
-1Nickel nitrate solution and 30ml concentration be 1molL
-1Cobalt nitrate solution change the 240ml nickel nitrate solution into, be this comparative example.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
Comparative example 8
The method preparation that this routine catalyst is provided according to patent CN1389545A.Evaluate catalysts under reaction condition the hydrocracking conversion ratio and the selectivity of crackate see Table 3.
The physico-chemical property of each routine catalyst of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Heteropoly acid have a phase | The Keggin structure | The Keggin structure | The Keggin structure | The Keggin structure |
| Chemical composition | ||||
| Used heteropoly acid, Wt% | 50 | 70 | 20 | 50 |
| Used carrier, Wt% | 41 | 31 | 51 | 41 |
| Ni，Wt％ | 5 | 5 | 5 | 5 |
| Co，Wt％ | 1 | 1 | 1 | 1 |
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Heteropoly acid have a phase | The Keggin structure | The Keggin structure | The Keggin structure | The Keggin structure |
| Chemical composition | ||||
| Used heteropoly acid, Wt% | 50 | 50 | 50 | 50 |
| Used carrier, Wt% | 41 | 41 | 41 | 34 |
| Ni，Wt％ | 5 | 5 | 5 | 10 |
| Co，Wt％ | 1 | 1 | 1 | 1 |
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Heteropoly acid have a phase | The Keggin structure | The Keggin structure | The Keggin structure | The Keggin structure |
| Chemical composition | ||||
| Used heteropoly acid, Wt% | 50 | 50 | 50 | 50 |
| Used carrier, Wt% | 41 | 41 | 30 | 37 |
| Ni，Wt％ | 5 | 5 | 18 | 5 |
| Co，Wt％ | 1 | 1 | 2 | 3 |
Table 2. feedstock property and reaction process condition thereof
| Raw material | N-decane |
| Reaction pressure, MPa | 2.0 |
| WHSV，h -1 | 4.94 |
| Hydrogen to oil volume ratio | 1500 |
| Reaction temperature, ℃ | 300 |
| Curing temperature, ℃ | 300 |
The hydrogenation cracking activity of each routine catalyst of table 3. and selectivity
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The n-decane conversion ratio, % | 47.3 | 35.7 | 24.3 | 60.9 | 37.7 |
| C 5+ selectivity, % | 70.7 | 62.5 | 74.5 | 77.1 | 65.3 |
| Catalyst | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| The n-decane conversion ratio, % | 44.4 | 30.7 | 67.5 | 42.1 | 42.2 |
| C 5+ selectivity, % | 63.8 | 65.2 | 73.7 | 69.1 | 71.3 |
| Catalyst | Embodiment 11 | Embodiment 12 | |||
| The n-decane conversion ratio, % | 27.4 | 43.4 | |||
| C 5+ selectivity, % | 68.9 | 70.9 | |||
| Catalyst | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| The n-decane conversion ratio, % | 37.7 | 32.3 | 31.9 | 50 | 29.4 |
| The C5+ selectivity, % | 70.5 | 65.7 | 62.1 | 70.3 | 61.8 |
| Catalyst | Comparative example 6 | Comparative example 7 | Comparative example 8 | ||
| The n-decane conversion ratio, % | 34.4 | 40.7 | 31.7 | ||
| The C5+ selectivity, % | 69.9 | 72.3 | 72.3 |
Claims (9)
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| CN100584458C CN100584458C (en) | 2010-01-27 |
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| CN101890346B (en) * | 2009-05-19 | 2013-06-05 | 中国石油化工股份有限公司 | Heteropoly acid catalyst and preparation method thereof |
| CN103861647A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing heteropoly acid and application thereof |
| CN107297223A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN107297224A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
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| US5350501A (en) * | 1990-05-22 | 1994-09-27 | Union Oil Company Of California | Hydrocracking catalyst and process |
| CN1159103C (en) * | 2002-06-17 | 2004-07-28 | 中国科学院山西煤炭化学研究所 | Low-temperature catalyst for producing middle distillates from heavy alkanes and preparation method thereof |
| FR2844726B1 (en) * | 2002-09-25 | 2004-12-03 | Atofina | CATALYTIC PROCESS FOR THE MANUFACTURE OF MERCAPTANS FROM THIOETHERS |
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| CN102933298A (en) * | 2009-12-16 | 2013-02-13 | Ifp新能源公司 | Catalysts comprising Group VIII and VIB metals useful in hydrotreating and process for their preparation using acetic acid and C1-C4 dialkyl succinates |
| CN102933298B (en) * | 2009-12-16 | 2016-08-03 | Ifp新能源公司 | Catalysts comprising Group VIII and VIB metals useful in hydrotreating and process for their preparation using acetic acid and C1-C4 dialkyl succinates |
| CN103861647A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing heteropoly acid and application thereof |
| CN103861647B (en) * | 2012-12-10 | 2016-01-20 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing heteropoly acid and application thereof |
| CN107297223A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN107297224A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN107297223B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN107297224B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN110026240A (en) * | 2017-12-13 | 2019-07-19 | Ifp 新能源公司 | Slurry hydroconversion process for heavy hydrocarbon feedstocks |
| CN110026240B (en) * | 2017-12-13 | 2023-07-11 | Ifp 新能源公司 | Slurry Hydroconversion Process for Heavy Hydrocarbon Feedstock |
| CN111744496A (en) * | 2020-07-31 | 2020-10-09 | 齐齐哈尔大学 | A kind of self-supporting composite electrode material and its preparation method and application |
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