CN1207369C - Catalyst for hydrogenation of olefin-containing naphtha and its preparing method - Google Patents
Catalyst for hydrogenation of olefin-containing naphtha and its preparing method Download PDFInfo
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- CN1207369C CN1207369C CN 03148500 CN03148500A CN1207369C CN 1207369 C CN1207369 C CN 1207369C CN 03148500 CN03148500 CN 03148500 CN 03148500 A CN03148500 A CN 03148500A CN 1207369 C CN1207369 C CN 1207369C
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Abstract
The present invention relates to hydrotreating catalyst of olefin-containing petroleum naphtha and a preparation method thereof. In the catalyst, a macropore acidic zeolite molecular sieve or a mesoporous acidic zeolite molecular sieve is mainly used, and the catalyst comprises 40 to 80 wt% of acidic zeolite molecular sieve, 0 to 60 wt% of gamma-Al2O3, and 0 to 20 wt% of group VIB metals and group VIII metals. The catalyst has outstanding hydrodesulphurization performance and outstanding aromatization performance. The catalyst of the present invention can obviously reduce the olefine content while reducing the sulfur content of the olefin-containing petroleum naphtha, and the catalyst has a powerful aromatization function. The whole process is completed in a single working procedure, and the octane value of the hydrogenated naphtha fraction is reduced a little or is not reduced. The catalyst without any harmful substances has the advantages of outstanding catalytic activity and favorable stability.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method that is used for the olefinic naphtha hydrotreatment, it is to belong to the catalyzer of olefinic naphtha hydrotreatment and preparation technology's innovation, more precisely about in the improvement that contains in the presence of the catalyzer of acid zeolite the hydroprocessing technique of olefinic naphtha.This catalyzer not only can reduce sulphur content and olefin(e) centent in the petroleum naphtha simultaneously, and can increase the content of aromatic hydrocarbons, makes that the octane value of petroleum naphtha does not reduce or reduces seldom behind the hydrogenation.
Technical background
As everyone knows, because the atmospheric pollution that the vehicle engine exhaust gas discharging causes is the key point that causes environmental problem.The sulphur content that effectively reduces in the gasoline is the important channel that solves air pollution problems inherent, and the catalytic cracking olefinic naphtha is the main source of sulfur in gasoline.Along with fast development of national economy and to the pay attention to day by day of environment protection, more and more higher to the requirement of vehicle fuel quality.Following gasoline development trend in the whole world will be considered the environmental protection of 21 century and the development of energy double influence and alternate-engine.At present, in the reduction petroleum naphtha there be the method for sulphur content: 1. to cracking or the unitary full feedstock hydrofining of coking, 2. to these unitary products, carry out hydrogenation such as petroleum naphtha.First kind of selection is because need huge hydrotreater and a large amount of hydrogen consumptions, and be costly.Second kind of selection is shortcut but can causes alkene (account for the 20～60v%) saturated of raw material usually, this also can reduce the gasoline products octane value and reaches 5-10 unit simultaneously.Loss of octane number when therefore how to reduce catalytic cracking olefinic naphtha hydrogenation is a bigger technical barrier, mainly contains following several technology at present.
1. adopt traditional Hydrobon catalyst, need earlier petroleum naphtha to be divided into weight two portions, the part of counterweight is carried out hydrogenation, and the light part that will tell is again mixed with the part of the weight of process hydrogenation.U.S.Pat.No.3,57,625 have invented a kind of method that reduces sulphur content in the naphtha products, and this method comprises that (1) heats up in a steamer gasoline fraction in 180～300 punishment of cut point becomes high boiling part and lower boiling part, and (2) are with high boiling part and a kind of Co-Mo/Al
2O
3The desulfurization catalyst contact, described catalytic temperature, pressure and air speed can effectively be carried out desulfurization, and reduce the content of alkene in the desulfurization product indistinctively; (3) lower boiling that (2) desulfurization product that obtains of step and (1) step are obtained and the product that is rich in alkene mix, and obtain a kind of sulphur content minimizing and have high-octane desulfurization product.
2. use and have the zeolite of medium hole dimension as isomerized catalyzer, and the product that carries out hydrogenation carried out octane value recovering, US Pat.No.5298150,5320742,5326462,5500108,5554274,599439 etc. for example, in these methods, for the loss that makes octane value in hydrogenation process reduces, must be through two step operation sequences, the first step is to use suitable desulfurization catalyst to carry out desulfurization, and the second step operation is to use the catalyzer that can make octane value recovering.
3. the hydrogen addition technology of skeletal isomerization and reduction alkene also can reduce the loss of octane value in the hydrogenation process, the selective hydrogenation that Here it is often says.US5,266,188 liters a kind of selective hydrodesulfurization method of hydrotreated feed, this method is included in 300～700 of temperature of reaction, under the existence of reaction pressure 50～600psig and a kind of catalyzer, with described charging and H-H reaction, described catalyzer contains a kind of hydrogenation component and a kind of carrier component, described hydrogenation component comprises a kind of group vib metal component and a kind of VIII family metal component, the content of described group vib metal component is 4～20 heavy %, and the content of VIII family metal component is 0.5～10 heavy %; Described carrier component contains the magnesium component of 0.5～50 heavy % and the alkaline components of 0.02～10 heavy %.
4. the traditional catalyst of olefinic naphtha hydrotreatment comprises and is supported on γ-Al
2O
3On the metal oxide catalyst of CoMo, NiMo, NiW, CoMoP and NiMoP.The tradition hydrotreating catalyst is when reducing The product sulfur content, and alkene is saturated in a large number, causes a large amount of losses of octane value, and this causes very big financial loss to the refinery.Purpose of the present invention is exactly at the saturated problem of alkene, by the content of increase aromatic hydrocarbons, thereby remedies because the saturated loss of octane number that causes of alkene.
Summary of the invention
Purpose of the present invention provides a kind of Catalysts and its preparation method that is used for the olefinic naphtha hydrotreatment with regard to being to avoid the deficiencies in the prior art part.This is a kind ofly significantly not reduce the olefinic naphtha hydrotreating catalyst that contains acid zeolite of the octane value of product when reducing the olefinic naphtha sulphur content.This catalyzer mainly is to contain macropore or mesopore acidic zeolite, and the proportioning of its each composition is: acidic zeolite: 40～80wt%; γ-Al
2O
3: 0～50wt%; The oxide compound of group vib metal M o and the oxide compound of group VIII metal Co are 0～20wt%.Its CoO and MoO
3Content is preferably 5～15wt%, and the Mo/Co atomic ratio is 1～6: 1, is preferably 2～3: 1.
This Preparation of catalysts be by adopt pickling process or dry mix with metal load on carrier.Its preparation method is:
1. employing pickling process: with roasting good contain acid zeolite and alumina supporter one or many dipping.All catalyst preparation process may be summarized to be following several steps: the 1. preparation of support of the catalyst, and 2. metal salt solution (as nitrate, carbonate, molybdate etc.) preparation, 3. dipping is 4. dry, 5. roasting.After adding metal component, the carrier of carrying metal is dry under 50～150 ℃, is preferably 80～120 ℃, reach 0.5～24h (being preferably 4～6h) as 120 ℃ of following dryings, (be preferably 450～550 ℃ at 400～600 ℃ then as 5h, as 500 ℃) following roasting 1～8h, be preferably 2～6h, as 5h.
2. it is direct to be used in the method for mixing: mixed by following material: metal-salt, as Xiao Suangu, ammonium molybdate etc.; Acidic molecular sieve is as ZSM-5; Inert support is as aluminum oxide; Water and acid are as nitric acid.After grinding, mixture is forged or pushes, and diameter is about 0.8～2.0mm (such as 1.6mm) and length is the bar of 2.5-15mm (such as 3.8mm) to form.80～150 ℃ of down dry 10～30 hours (being preferably 12～24h), then 400～600 ℃ of following roastings (being preferably 450～550 ℃), 2～8h (being preferably 4～6h) as 5h as 500 ℃ as 16h.
The carrier that contains zeolite and aluminum oxide need pass through ammonium (as ammonium nitrate) exchange with displacement Na ion, the method of ammonium exchange exchanges after can adopting preceding exchange of moulding or moulding, concrete grammar is: the carrier that contains zeolite that adds zeolite molecular sieve powder or moulding in the ammonium nitrate solution of 1 mol of about 10 times of zeolite volumes, stir exchange 4 hours, static, separate, use distilled water flushing three times, baking 10 hours in 120 ℃ of baking ovens then, 500 ℃ of following roastings 4 hours; Repeat above-mentioned steps three times, get hydrogen type molecular sieve.
In the catalyzer for preparing, metal content percentage ratio is represented by the percentage that metal accounts for total catalyst weight.
Embodiment
Come enumeration technical characterstic of the present invention below in conjunction with inventive embodiment.
Example 1～4th, the preparation method of support of the catalyst of the present invention.
Embodiment 1 takes by weighing 90 parts former powder of ZSM-5 and 60 parts pseudo-boehmite (the German CONDEA product SB of company powder), the sesbania powder that adds 3 parts, mix, aqueous nitric acid with 2% mixes pinches into even mashed prod, pinch through mixing, extrusion, make the bar of diameter 1.6mm, under infrared lamp behind the dry 5h, put in the baking oven and descended 500 ℃ of roasting 5h in muffle furnace dry 10 hours at 120 ℃.The carrier concentration that roasting is good is that the ammonium nitrate solution of 1mol/l carries out the ammonium exchange, the two volume ratio is 1: 10,4～12 hours swap time, use distilled water flushing afterwards 3 times, 120 ℃ of dryings 10 hours, 500 ℃ of following roastings 4 hours, this process repeat to obtain containing for four times the carrier A of acid HZSM-5.The BET specific surface area of carrier A is 333.34m
2/ g, pore volume are 0.20cm
3/ g, mean pore size is 3.52nm,
Example 2～4 changes the content of former powder of ZSM-5 and SB powder respectively according to the step of example 1, makes acid carrier B, C and the carrier D of different ZSM-5 content, and the composition (mass content) behind its deduction moisture is as shown in table 2.
The composition of table 2 carrier
Carrier A B C D
ZSM-5％ 65.2 74.4 83.3 91.8
γ-Al
2O
3％ 34.8 25.6 16.7 8.2
Example 5～8th, the preparation method of support of the catalyst of the present invention.
Example 5 takes by weighing the 6.96g carrier A, takes by weighing Xiao Suangu 0.40g and dissolves in the 5ml distilled water, pour in the cobalt nitrate solution carrier A into dipping 8h after, (120 ℃) dry 12h in baking oven, 500 ℃ of roasting 4h in muffle furnace then again; Take by weighing the 0.73g ammonium molybdate and dissolve in the 5ml distilled water, with load the carrier A of Xiao Suangu pour in the ammonium molybdate solution behind the dipping 8h, (120 ℃) dry 12h in baking oven again, 500 ℃ of roasting 4h in muffle furnace then, last porphyrize sieves out 20-40 purpose particle.Can make catalyst A 10.
According to above-mentioned same method, use carrier B, C and carrier D to make catalyst B 10, C10 and D10 respectively.
Example 6 takes by weighing alumina supporter 9.52g, takes by weighing Xiao Suangu 0.55g and dissolves in the 10ml distilled water, pour in the cobalt nitrate solution carrier into dipping 8h after, (120 ℃) dry 12h in baking oven, 500 ℃ of roasting 4h in muffle furnace then again; Taking by weighing the 1.00g ammonium molybdate dissolves in the 10ml distilled water, with load the alumina supporter of Xiao Suangu pour in the ammonium molybdate solution behind the dipping 8h, (120 ℃) dry 12h in baking oven again, 500 ℃ of roasting 4h in muffle furnace then, last porphyrize sieves out 20-40 purpose particle.Can make comparative catalyst DB.
Example 7 takes by weighing the 10.24g carrier A, takes by weighing Xiao Suangu 0.35g and dissolves in the 10ml distilled water, pour in the cobalt nitrate solution carrier A into dipping 8h after, (120 ℃) dry 12h in baking oven, 500 ℃ of roasting 4h in muffle furnace then again; Take by weighing the 0.64g ammonium molybdate and dissolve in the 10ml distilled water, with load the carrier A of Xiao Suangu pour in the ammonium molybdate solution behind the dipping 8h, (120 ℃) dry 12h in baking oven again, 500 ℃ of roasting 4h in muffle furnace then, last porphyrize sieves out 20-40 purpose particle.Can make catalyst A 6.
Example 8 takes by weighing the 10.44g carrier A, takes by weighing Xiao Suangu 0.84g and dissolves in the 10ml distilled water, pour in the cobalt nitrate solution carrier A into dipping 8h after, (120 ℃) dry 12h in baking oven, 500 ℃ of roasting 4h in muffle furnace then again; Take by weighing the 1.53g ammonium molybdate and dissolve in the 10ml distilled water, with load the carrier A of Xiao Suangu pour in the ammonium molybdate solution behind the dipping 8h, (120 ℃) dry 12h in baking oven again, 500 ℃ of roasting 4h in muffle furnace then, last porphyrize sieves out 20-40 purpose particle.Can make catalyst A 14.
The composition of each catalyzer is as shown in table 3, and each content all has calculating and gets.
Table 3
| The catalyzer numbering | A6 | A10 | A14 | B10 | C10 | D10 | DB |
| CoO，％ | 0.83 | 1.34 | 1.82 | 1.34 | 1.34 | 1.34 | 1.34 |
| MoO 3，％ | 4.81 | 7.77 | 10.48 | 7.77 | 7.77 | 7.77 | 7.77 |
| ZSM-5，％ | 61.52 | 59.26 | 57.18 | 67.62 | 75.71 | 83.43 | 0 |
| γ-Al 2O 3，％ | 32.84 | 31.63 | 30.52 | 23.27 | 15.18 | 7.45 | 90.89 |
The invention effect
The accessible raw material of the present invention can be olefinic naphtha, the full range olefinic naphtha that normally from catalytic cracking and coking unit operations, gets, can be straight-run naphtha, thermal naphtha etc. also, the described naphtha that contains alkene be preferably catalytic cracking naphtha or coking naphtha.
Catalyst provided by the invention is in the hydrotreatment process that is used for olefinic naphtha, the process conditions that are suitable for are the common process condition that petroleum naphtha hydrogenation is processed, need to process through presulfurization such as catalyst, curing temperature is 260～450 ℃, cure time is 8-48 hour, and hydrogen to oil volume ratio is 100～500.
Claims (4)
1. a catalyzer that is used for the olefinic naphtha hydrotreatment contains macropore or mesopore acidic zeolite in its composition, it is characterized in that the weight ratio of each composition is:
Acidic zeolite: 40～80%;
γ-Al
2O
3：0～60％；
The oxide compound of group vib metal M o and the oxide compound of group VIII metal Co: 0～20%.
2. the catalyzer that is used for the olefinic naphtha hydrotreatment according to claim 1 is characterized in that described zeolite is the ZSM-5 molecular sieve, and needs to make hydrogen type molecular sieve through ammonium exchange processing.
3. the catalyzer that is used for the olefinic naphtha hydrotreatment according to claim 1 is characterized in that the oxide compound of described group vib metal M o and the oxide compound of group VIII metal Co are CoO and MoO
3, the atomic ratio of its Mo/Co is 1～6: 1.
4. Preparation of catalysts method that is used for the olefinic naphtha hydrotreatment, it is to adopt pickling process or dry mix to come the loaded metal component, it is characterized in that the catalyzer behind the loaded metal must be through roasting and sulfidizing, maturing temperature is that 300-600 ℃, time are 2-8 hour; Curing temperature is 260-450 ℃, and curing time is 8-48 hour, and hydrogen to oil volume ratio is 100～500.
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| CN1207369C true CN1207369C (en) | 2005-06-22 |
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