CN100348317C - Aromatic hydrocarbon hydrogenation catalyst and its preparation method - Google Patents

Abstract

The present invention relates to an aromatic hydrogenation catalyst and a preparation method thereof, and provides an aromatic hydrogenation catalyst with high hydrogenation activity and sulfur poisoning resistance and a simple preparation method. The aromatic hydrogenation catalyst comprises ingredients of nickel oxide, boron oxide and tungsten oxide. The preparation method comprises the steps: weighing nickel carbonate or basic nickel carbonate powder, adding a boric acid solution at the concentration of 1.0 mol/L in the nickel carbonate powder, adding tungstic acid or ammonium metawolframate powder or an ammonium metawolframate solution, mixing, drying, roasting and tabletting materials. The preparation process is shortened and the operation is simplified. The catalyst has pore volume larger than 0.18 cu cm/g, specific surface area greater than 180 sq m/g, high hydrogenation activity and high sulfur poisoning resistance, and is suitable for the aromatic hydrogenation reaction process. With the same evaluation device and under the same condition, when noble metal Ru loaded by activated carbon is used as a catalyst, the ethylenzene conversion rate is only 7.8%.

Description

A kind of aromatic hydrocarbon hydrogenation catalyst and preparation method thereof

Technical field

The present invention relates to a kind of aromatic hydrocarbon hydrogenation catalyst and preparation method thereof.

Background technology

The aromatic hydrogenation technology plays important effect on petrochemical industry.High arene content brings many problems in the oil product, can increase particle emission in the diesel combustion waste gas, weighting ring environment pollution as the raising of arene content in the diesel oil.Owing to all contain a certain amount of sulfide in the oil product, so in hydrogenation process, be subjected to the influence of sulfur poisoning inevitably.At present, China's fuel oil ubiquity sulfide and arene content problem of higher need to be resolved hurrily.Therefore, the research and development of anti-sulphur high activity aromatic hydrocarbon hydrogenation catalyst are one of hot issues of current catalytic field common concern.

The core of aromatic hydrogenation technology is a catalyst.Aromatic hydrocarbon hydrogenation catalyst can be divided into two classes, and a class is a metallic catalyst, comprises noble metal catalyst and non-precious metal catalysts such as Ni, Co such as Pt, Pd; One class is a sulfide type catalyst.The advantage of last class catalyst is the aromatic hydrogenation activity height, and shortcoming is easily to be poisoned by sulfur-containing compound.Back one class catalyst antithesis, the sulfur poisoning-resistant ability is good, but hydrogenation activity is very low.In addition, noble metal catalyst is gone back ortho states or sulphided state and is all existed and cost an arm and a leg, and is unfavorable for the problem of suitability for industrialized production.Therefore, the high non-precious metal catalyst of the development good activity of sulfur resistance will be of great importance.

U.S. Pat 5258346 has disclosed the aromatic hydrocarbon hydrogenation catalyst of a kind of Ni of reduction as active component, can be applicable to various oil products especially than the hydrogenation aromatics-removing of heavy-hydrocarbon oil.This patent thinks that the sulfur poisoning-resistant ability key of Ni/ supported catalyst is to improve pore size distribution.Even like this, the anti-sulfuration ability of this patent catalyst also is limited, in industrial application certain difficulty is arranged obviously.

Patent CN1044379C discloses a kind of preparation method of aromatic hydrocarbon hydrogenation catalyst.This method be with behind the aluminium-hydroxide powder extruded moulding with containing SiF ₆ ^2-Solution impregnation, 550～750 ℃ of activation obtain carrier, and then load Ni, W active component make catalyst.This catalyst is calculated to such an extent that consist of by weight: NiO 1.0%～5.0%, WO ₃15.0%～35.0%, F 0.5%～6.0%, SiO ₂0.3%～5.0%, all the other are Al ₂O ₃

U.S. Pat 4957895 provides a kind of aromatic hydrogenation to handle the Preparation of catalysts method, is with H ₂SiF ₆The aqueous solution or H ₂SiF ₆The mixed aqueous solution of the aqueous solution and nitric acid is blended into and mixes alunite in the aluminium hydrate powder, and dry again behind the extruded moulding, roasting makes catalyst.This catalyst carrier is made up of 1.0%～10.0% fluorine, 0.5%～5.0% silica and 85%～99% aluminium oxide, and active component is Ni, W.

Need vulcanize before above-mentioned two patent catalyst use, its aromatic hydrogenation activity is lower.

Summary of the invention

It is simple that purpose of the present invention aims to provide a kind of preparation method, has aromatic hydrocarbon hydrogenation catalyst of higher hydrogenation activity and sulfur poisoning-resistant ability and preparation method thereof simultaneously.

Aromatic hydrocarbon hydrogenation catalyst main component of the present invention comprises nickel oxide, boron oxide and tungsten oxide, and the percentage composition of each component is (is to calculate benchmark with the catalyst weight):

NiO:50%～80%, B ₂O ₃: 1.5%～8.0%, WO ₃: 18%～45%, the pore volume of catalyst is greater than 0.18mlg ^-1, surface area is greater than 180m ²G ^-1

The preparation method of aromatic hydrocarbon hydrogenation catalyst of the present invention is as follows:

1) be 1.0molL with concentration ^-1BAS add in nickelous carbonate or the basic carbonate nickel by powder;

2) take by weighing wolframic acid or ammonium paratungstate powder or ammonium metatungstate solution by the catalytic component proportioning, add in the step 1 in the gained material;

3) the gained material is mixed, dry 5h down at 100～120 ℃;

4) with step 3 gained material at 350～450 ℃ of following roasting 3～5h;

5) with the material compression molding after the roasting, promptly get final catalyst.

Flow-type differential reactor-gas phase chromatographic device is adopted in evaluation to catalyst.In reaction pressure is that 2.0Mpa, temperature are that 200 ℃, liquid air speed are 2.0h ^-1, hydrogen to oil volume ratio is under 3000 the condition, to contain 120mgL ^-1CS ₂Ethylbenzene when being reaction raw materials, the conversion ratio of ethylbenzene is greater than 15.0%.

The present invention adopts the preparation method who directly three kinds of components of catalyst is mixed, and preparation process shortens, simplified control.The catalyst pore volume of preparation is greater than 0.18cm ³G ^-1, specific area is greater than 180m ²G ^-1, be applicable to the aromatic hydrogenation course of reaction, have the active and stronger sulfur poisoning-resistant ability of higher hydrogenation reaction.Adopt identical evaluating apparatus, under the same conditions with activated carbon supported noble metal Ru during as catalyst, conversion of ethylbenzene has only 7.8%.

The specific embodiment

Further specify the present invention below by embodiment.

Embodiment 1

Take by weighing basic carbonate nickel by powder 84.75g, add 1.0molL ^-1BAS 36.0mL, add 1.0molL again ^-1Ammonium metatungstate solution 64.0mL, above-mentioned mixing of materials is even.With mixed material at 100 ℃ of following oven dry 5h, again with material at 350 ℃ of following roasting 5h.Material compression molding after the roasting is obtained catalyst, and it consists of (being to calculate benchmark with the catalyst weight): NiO=75.6%, B ₂O ₃=1.9%, WO ₃=22.5%.The average pore size of catalyst A is 5.30nm, and pore volume is 0.278mlg ^-1, specific area is 242m ²G ^-1It is formed and character sees Table 1.

Catalyst hydrogenation reactivity evaluation experimental adopts flow-type differential reactor-gas phase chromatographic device as the activity rating device.Reaction raw materials is for containing 120mgL ^-1The ethylbenzene liquid of carbon disulfide.Earlier with catalyst at 400 ℃, reduce 3h under the nitrogen atmosphere, and then feed reaction raw materials and carry out hydrogenation reaction.Reaction condition is pressure 2.0MPa, 200 ℃ of temperature, ethylbenzene liquid air speed 2.0h ^-1, hydrogen to oil volume ratio 3000 is taken a sample behind the reaction 3h.Ethylbenzene hydrogenation activity evaluation result sees Table 2.

The result as can be seen, prepared catalyst is compared with ruthenium is noble metal catalyst based, has hydrogenation activity and sulfur poisoning-resistant ability preferably.

Table 1 embodiment 1～4 product main character

Embodiment	NiO ％	B 2O 3 ％	WO 3 ％	Average pore size nm	Pore volume mlg -1	Specific area m 2·g -1
							1	75.6	1.9	22.5	5.30	0.278	242
2	62.7	6.3	31.0	4.48	0.190	200.
							3	63.6	4.8	31.6	4.49	0.265	195
4	56.5	4.3	39.2	5.17	0.290	190

Embodiment 2

Preparation process such as embodiment 1 take by weighing basic nickel carbonate 84.75g, add 1.0molL ^-1BAS 144.0mL, add 1.0molL again ^-1Ammonium metatungstate solution 107.0mL, mix the back at 100 ℃ of following oven dry 5h, again at 450 ℃ of roasting 3h.Compression molding obtains catalyst, and it is formed and character sees Table 1.

Activity of such catalysts is estimated with embodiment 1, the results are shown in Table 2.

Embodiment 3

Preparation process such as embodiment 1 take by weighing basic nickel carbonate 84.75g, add 1.0molL ^-1BAS 108.0mL, add ammonium paratungstate powder 27.90g again, mix the back at 450 ℃ of following roasting 5h.Compression molding obtains catalyst C, and it is formed and character sees Table 1.

Activity of such catalysts is estimated with embodiment 1, the results are shown in Table 2.

Embodiment 4

Preparation process such as embodiment 1 take by weighing basic nickel carbonate 93.0g, add 1.0molL ^-1BAS 108.0mL, add wolframic acid powder 37.38g again, mix the back at 400 ℃ of following roasting 5h.Compression molding obtains catalyst D, and it is formed and character sees Table 1.

Reference example

Take by weighing 30.0g processed active carbon, with containing 1.0gRuCl ₃The solution impregnation active carbon, preparation contains the catalyst of w (Ru)=5%, in 110 ℃ of oven dry down, making active carbon is the Ru catalyst of carrier then.Adopt identical evaluating apparatus, under the same conditions catalyst is carried out activity rating, conversion of ethylbenzene has only 7.8% (seeing Table 2).

Table 2 activity of such catalysts evaluation result

Embodiment	Conversion of ethylbenzene/%
		1	19.6
2	24.2
		3	16.2
4	15.3
		Reference example	7.8

Claims (2)

1. aromatic hydrocarbon hydrogenation catalyst is characterized in that its composition is made up of nickel oxide, boron oxide and tungsten oxide, is that the percentage composition that calculates each component of benchmark is with the catalyst weight:

NiO：50％～80％，

B ₂O ₃：1.5％～8.0％，

WO ₃：18％～45％。

2. the preparation method of a kind of aromatic hydrocarbon hydrogenation catalyst as claimed in claim 1 is characterized in that the steps include:

1) be 1.0molL with concentration ^-1BAS add in nickelous carbonate or the basic carbonate nickel by powder;

2) take by weighing wolframic acid or ammonium paratungstate powder or ammonium metatungstate solution by the catalytic component proportioning, add in the step 1 in the gained material;

3) the gained material is mixed, dry 5h down at 100～120 ℃;

4) with step 3 gained material roasting 3～5h under 350～450 ℃ condition;

5) with the material compression molding after the roasting, promptly get final catalyst.