CN1191332C - Reformed oil olefine saturation hydrogenation method - Google Patents
Reformed oil olefine saturation hydrogenation method Download PDFInfo
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- CN1191332C CN1191332C CNB011202319A CN01120231A CN1191332C CN 1191332 C CN1191332 C CN 1191332C CN B011202319 A CNB011202319 A CN B011202319A CN 01120231 A CN01120231 A CN 01120231A CN 1191332 C CN1191332 C CN 1191332C
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Abstract
The present invention relates to a reformed oil olefine saturation hydrogenation method. The method comprises that under the existence of a catalyst, reformed oil is in contact with hydrogen, the contacted temperature is from 200 to 320 DEG C, the contacted pressure is not less than 0.7MPa, the liquid hourly space velocity is from 1 to 8 h<-1>, and the volume ratio of the hydrogen and the oil is not less than 30. The catalyst comprises tungsten oxide and/or molybdenum oxide, nickel oxide and cobalt oxide which are loaded on an alumina carrier, and uses the catalyst as the reference. The weight percentage of the content of the tungsten oxide and/or the molybdenum oxide is less than 10%, the weight percentage of the content of the nickel oxide is from 1 to 5%, the weight percentage of the content of the cobalt oxide is from 0.01 to 1%, and the ratio of the total atomicity of nickel and cobalt and the total atomicity of nickel, cobalt, tungsten and/or molybdenum is 0.3 to 0.9.
Description
Technical field
The invention relates to a kind of olefine saturation hydrogenation method, more particularly, is optionally the alkene in the reformed oil to be carried out hydrogenation about a kind of, to reduce the reformed oil olefine saturation hydrogenation method of olefin(e) centent in the reformed oil.
Background technology
Catalytic reforming is one of main technique of producing in stop bracket gasoline and light aromatic hydrocarbons, in the reforming process of petroleum naphtha, because the high-temperature dehydrogenation reaction takes place, therefore can generate a spot of alkene, particularly in the continuous reforming process process, owing to operate under the condition of high-temperature low-pressure, the alkene of generation is more, and the olefin(e) centent in the reformed oil can be higher.For being the catalytic reforming process of purpose to produce aromatic hydrocarbons, the existence of small amounts of olefins promptly can influence the colourity and the stability of reformed oil product.Therefore, the alkene in the reformed oil must be removed.In addition, the reforming raffinate oil that reformed oil obtains after the aromatic hydrocarbons extracting is a raw material of producing solvent oil, in order to produce qualified solvent oil, the olefin(e) centent in the reforming raffinate oil also must be reduced, and makes reforming raffinate oil satisfy the specification of quality that the bromine valency is lower than 0.5gBr/100g.
At present, remove that the technology of small amounts of olefins mainly contains two kinds in the reformed oil, promptly clay-filtered technology and hydrogenation technique.
Clay-filtered technology is the alkene that utilizes in the carclazyte absorption aromatic hydrocarbon product, to reach the purpose of removing alkene, the carclazyte activity is lower, adsorber is huge owing to exist, and shortcomings such as environmental pollution and air speed are lower are lacked, easily caused to life cycle, thereby this technology has the trend that is replaced by hydrogenation technique.
Hydrogenation technique can be divided into two kinds again, first kind is traditional back end hydrogenation technology, the flow process of this technology is, the generation oil of last reforming reactor outlet and hydrogen are through an interchanger, fluid temperature (F.T.) is reduced to about 330 ℃, enter the back end hydrogenation reactor that hydrogenation catalyst is housed then, make the hydrogenation of olefins that generates in the oil.Flow process is simple, energy consumption is low though back end hydrogenation technology has, do not have advantages such as " three wastes ".But along with progressively applying of two (many) metal reforming catalysts in recent years, the raising of resurfacing operation severity, this technology can influence the water chloride balance control of reforming catalyst, the pressure drop of increase recycle hydrogen system.And, because its temperature of reaction is higher, always there is the part aromatic hydrocarbons in the reformed oil saturated by hydrogenation.Second kind is that reforming raffinate oil is carried out hydrogenation, because aromatic free in the reforming raffinate oil, therefore there is not the aromatic hydrocarbons loss, still, at present, the catalyzer that is used for the reforming raffinate oil hydrogenation is noble metal catalyst, the cost of catalyzer is higher, simultaneously, because the easy poisoning and deactivation of noble metal catalyst, therefore, adopt this technology strict to impurity in the reforming raffinate oil raw material.
CN85,104,438B discloses tungsten and the nickel catalyzator that a kind of fluoro-containing alumina that is used for fraction oil hydrogenation refining supports, this catalyzer gama-alumina that to be the purity that obtained by aluminum alkoxide or alkyl aluminum hydrolysis obtain through 500-700 ℃ of roasting greater than the diaspore of 65 heavy % makes fluoro-containing alumina through the dipping fluorine cpd, re-uses the technology of soaking altogether, the catalyzer that the oxide compound of tungsten and nickel makes in the load equably, it consists of the heavy % of nickel oxide 1-5, the heavy % of Tungsten oxide 99.999 12-35, the heavy % of fluorine 1-9.Because this catalyst metal content is higher, thereby its cost is higher.This catalyzer is applicable to the hydrofining of distillate, i.e. desulfurization and denitrification process.
CN1,085,934A discloses a kind of catalyzer that is used for hydrorefining petroleum waxes, and this catalyzer is made up of magnesium oxide, nickel oxide, Tungsten oxide 99.999 and aluminum oxide, wherein, the heavy % of heavy %, tungsten oxide content 24.0-34.0 of content of magnesia 0.1-1.9 heavy %, nickel oxide content 2.5-6.0, this catalyzer is applicable to heavier petroleum fractions, is specially adapted to the unifining process of petroleum wax cut, and has higher hydrogenation activity, but its metal content is higher, and cost is higher.
CN1,105,053A discloses a kind of fraction oil Hydrobon catalyst, this catalyzer is made of the aluminum oxide precursor carrier that high-temperature roasting obtains under the gas mixture atmosphere of air and water vapour, fluorine auxiliary agent and nickel and tungsten active ingredient, each component concentration is (with the catalyzer is benchmark, weight %): fluorine 1-9%, nickel oxide 1-5%, Tungsten oxide 99.999 15-38%, all the other are carriers.This catalyzer is applicable to the hydrogenation process of heavy distillate, and has higher hydrogenation activity, but its metal content is higher, and carrier must be through air and the high-temperature roasting of water vapor mixture atmosphere, and preparation process is comparatively complicated, and therefore, cost is higher.
CN1,123, it is carrier with the gama-alumina that 310A discloses a kind of, active ingredient is the Hydrodevulcanizing catalyst for hydro-carbons of cobalt, molybdenum, described carrier modified zinc oxide, single-steeping cobalt-molybdenum, this catalyzer are formed (weight) and are: ZnO 1-15%, MoO
35-18%, CoO 1-10%.
CN1,040,610A discloses a kind of Hydrodevulcanizing catalyst for hydro-carbons, and it is to contain the γ-Al of titanium oxide
2O
3Be carrier, active ingredient is molybdenum, cobalt and nickel.γ-Al
2O
3Titanium oxide content is the heavy % of 5-30 in the carrier, MoO in the catalyzer
3Content is the heavy % of 5-20, and preferably 10-15 weighs %, and CoO content is the heavy % of 1-10, and NiO content is the heavy % of 2-10.This catalyzer can be used for boiling range 80-200 ℃, the hydrogenating desulfurization of the petroleum fractions of sulphur content 1-300ppm.
USP4880524 discloses a kind of temperature, 13.6-238 kilograms per centimeter at 149-482 ℃
2Pressure under by hydrocarbon feed being contacted the method for hydrocarbon feed being carried out hydrotreatment with a kind of catalyzer, at least 300 meters of the specific surfaces of described catalyzer
2/ gram, and bore dia accounts at least 70% of total pore volume less than the pore volume of 70 dusts.Described catalyzer adopts special method preparation, contains the nickel (amounting to into nickel oxide is the heavy % of 1.27-7.62) of the heavy % of 1-6, molybdenum (amounting to into molybdenum oxide is the heavy % of 12-35) or the heavy % tungsten of 10-40 (amounting to into Tungsten oxide 99.999 is the heavy % of 12.6-50.4) or the molybdenum of the heavy % of 8-40 and the mixture of tungsten of the heavy % of 8-22 in the catalyzer.This catalyst metal content is higher and preparation process is comparatively complicated.
CN1,169,337A discloses a kind of catalyst for hydrogenation of fraction oil, and this catalyzer contains tungsten, nickel and the cobalt that loads on the gama-alumina, and in oxide compound, W content is that the heavy % of 10-30, nickel content are that the heavy % of 1-7, cobalt contents are the heavy % of 0.01-1.This catalyzer is total to infuse fully with the aqueous solution of tungsten, nickel and cobalt compound.There is metal content shortcoming higher, that cost is higher equally in this catalyzer.
In addition, above-mentioned catalyzer all has a fatal shortcoming, is exactly that low temperature active is lower, and at low temperatures, the bromine valency of hydrogenation products can not satisfy the quality product requirement; And at high temperature, when adopting the whole generation of above-mentioned catalyst towards heavy oil to carry out olefine saturation hydrogenation, part aromatic hydrocarbons is also saturated by hydrogenation inevitably, causes the loss of part aromatic hydrocarbons.Therefore above-mentioned catalyzer is not suitable for being used for reformed oil is carried out the olefine saturation hydrogenation reaction.
Existing olefine saturation hydrogenation catalyzer summarize have following several, that is:
(1) Mo-Co-Al that uses of traditional reformed oil back end hydrogenation technology
2O
3Catalyzer, this catalyzer have equally that low temperature active is lower, and the bromine valency of hydrogenation products can not satisfy the quality product requirement, the loss important disadvantages of aromatic hydrocarbons under the high temperature.
(2) Raney nickel (RaneyNi) catalyzer is characterized in having higher activity, can catalysis low temperature (being lower than 220 ℃) the saturated hydrogenation reaction of alkene down.
(3) the non-loading type amorphous alloy catalyst of nickeliferous or cobalt or iron, comprising the olefine saturation hydrogenation activity apparently higher than the big surface amorphous alloy catalyst of Raney nickel (CN1,073,726A).
Because Raney nickel and amorphous alloy catalyst granularity all less (20 orders are following), be not suitable for fixed-bed reactor, and when being used for fluidized-bed reactor, granules of catalyst is easy to be taken out of by fluid, adopt the use of this catalyzer owing to a large amount of nickel and/or cobalt simultaneously, the cost of catalyzer is equally very high.And, because amorphous alloy catalyst inherent thermolability is restricted in industrial practical application
CN1,250,799A discloses a kind of reformed oil olefine saturation hydrogenation method, this method is included under a kind of existence of catalyzer reformed oil is contacted with hydrogen, the condition of described contact is temperature of reaction 50-200 ℃, and reaction pressure is greater than 0.1 MPa, liquid hourly space velocity 0.1-20 hour
-1, hydrogen to oil volume ratio is greater than 30; Described catalyzer is a kind of carried non-crystal alloy catalyst, this catalyzer contains a kind of porous carrier materials, a kind of group VIII metal and is selected from one or both elements in boron, the phosphorus, described group VIII metallic element exists with the form of the amorphous alloy of group VIII metal and B or group VIII metal and P and is carried in the porous carrier materials, the content of described group VIII metal and boron and/or phosphorus is the heavy % of 0.1-60, and the atomic ratio of group VIII metallic element and boron and/or phosphorus is 0.5-10.The concrete good low temperature active of this method catalyst system therefor, still, because amorphous alloy catalyst inherent thermolability is restricted in industrial practical application too.
Summary of the invention
The bromine valency that the objective of the invention is to overcome hydrogenation products under the art methods low temperature can not satisfy the quality product requirement, the loss important disadvantages of aromatic hydrocarbons under the high temperature, provide a kind of new bromine valency of hydrogenation products under lower temperature can satisfy the quality product requirement, the less reformed oil olefine saturation hydrogenation method of the loss of aromatic hydrocarbons under the high temperature.
As previously mentioned, in the prior art, though amorphous alloy catalyst has higher low temperature active, because its inherent thermolability, can not prolonged application in industry.And the low temperature active of traditional hydrogenation catalyst is all lower, and metal content is also higher, and cost is higher.The present inventor is surprised to find that, adopts CN1,229, and the catalyzer that 835A is disclosed carries out the saturated hydrogenation of alkene to reformed oil, and the bromine valency of hydrogenation products can satisfy the quality product requirement under lower temperature, and the loss of aromatic hydrocarbons is also less under the high temperature.This catalyzer is to introduce three active component nickel, cobalt and molybdenums and/or tungsten on catalyst carrier alumina, and adjusts three ratios between the component and obtain.Particularly adopt a kind of special methods to prepare this catalyzer and can further improve its low temperature active.
Method provided by the invention is included in a kind of catalyzer and exists down, and reformed oil is contacted with hydrogen, and the temperature of contact is 200-320 ℃, and the pressure of contact is for being not less than 0.7 MPa, and liquid hourly space velocity is 1-8 hour
-1, hydrogen to oil volume ratio is for being not less than 30; Described catalyzer contains Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide that loads on the alumina supporter, with the catalyzer is benchmark, the content of described Tungsten oxide 99.999 and/or molybdenum oxide is that 4 heavy % are to weighing % less than 10, the content of nickel oxide is the heavy % of 1-5, the content of cobalt oxide is the heavy % of 0.01-1, and nickel and cobalt total atom number are 0.3-0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum.
The bromine valency of method provided by the invention hydrogenation products under lower temperature (200-250 ℃) can satisfy the quality product requirement, the loss of aromatic hydrocarbons is less under the high temperature (＞250-320 ℃), the bromine valency that has overcome hydrogenation products under the prior art low temperature can not satisfy the quality product requirement, the loss important disadvantages of aromatic hydrocarbons under the high temperature.
For example adopt method provided by the invention, with containing the heavy % of cobalt oxide 0.05-0.25, the heavy % of nickel oxide 2.05-3.51, Tungsten oxide 99.999 or the heavy % of molybdenum oxide 6.06-8.50, nickel and cobalt total atom number are 55-165 ℃ with the catalyzer of the ratio 0.46-0.60 of the total atom number of nickel, cobalt, tungsten and/or molybdenum to boiling range, the bromine valency was that the reforming raffinate oil of 14.43gBr/100g carries out olefine saturation hydrogenation, hydrogen dividing potential drop 1.6 MPas, liquid hourly space velocity 3 hours
-1, hydrogen to oil volume ratio 150 condition under, when temperature of reaction is 230 ℃, the bromine valency of reaction product drops to below the 0.5gBr/100g, when temperature of reaction was 250 ℃, the bromine valency of reaction product dropped to below the 0.08gBr/100g, all meets the specification of quality of producing solvent oil, particularly, the low temperature active of catalyzer that soaks cobalt method preparation after the employing is higher, and soaks the method preparation of cobalt after adopting, and the catalyzer that contains auxiliary agent magnesium, phosphorus or fluorine simultaneously is wherein active the highest.
And adopt existing metal content higher, described nickel and cobalt total atom number and nickel, cobalt, the ratio of the total atom number of tungsten and/or molybdenum is (the cobalt oxide content 0.05 heavy % of the commercial catalysts within scope of the present invention not, nickel oxide content 2.4 heavy %, tungsten oxide content 20 heavy %, auxiliary agent Mg content 0.8 heavy %, nickel and cobalt atom number and nickel, the ratio of cobalt and tungsten total atom number is 0.27) and metal content (heavy % of nickel oxide content 6.5 of the commercial catalysts within the scope of the invention not, molybdenum oxide content 19.5 heavy %, auxiliary agent potassium content 0.49 heavy %, the ratio 0.39 of nickle atom number and the total atom number of nickel and molybdenum) commercial catalysts, under the identical situation of other reaction conditionss, when temperature of reaction is 230 ℃, the bromine valency of reaction product all can only drop to more than the 0.6gBr/100g, can not reach the specification of quality of producing solvent oil.Though two-pack reference catalyst (the nickel oxide content 3.62 heavy %s of the ratio that adopts nickle atom number and the total atom number of nickel and tungsten within the ratio scope of nickel of the present invention and cobalt total atom number and the total atom number of nickel, cobalt, tungsten and/or molybdenum, tungsten oxide content 8.53 weights, nickel is 0.56 with nickel and tungsten total atom ratio) time, under the identical situation of other reaction conditionss, when temperature of reaction was 230 ℃, the bromine valency of reaction product can only drop to more than the 0.8gBr/100g.
For example adopting method provided by the invention again, is 270 ℃ in temperature of reaction, and the hydrogen dividing potential drop is that 1 MPa, liquid hourly space velocity are 4 hours
-1, hydrogen to oil volume ratio is under 100 the condition, to boiling range is 48-181 ℃, the bromine valency is 3.25gBr/100g, aromaticity content is the saturated hydrogenation that the reformed oil of 55.57 heavy % carries out alkene, the bromine valency of reaction product all drops to below the 0.06gBr/100g, and aromaticity content can reach the heavy % of 55.05-55.56 in the product.Be that aromatic hydrocarbons does not have loss substantially.And when adopting above-mentioned three kinds of existing catalyzer, under same reaction conditions, though the bromine valency of reaction product also can drop to below the 0.08gBr/100g, aromaticity content but is reduced to the heavy % of 52.89-53.65 in the product, and aromaticity content obviously reduces in the product.
In addition, because method catalyst system therefor provided by the invention has the metal content lower than the prior art catalyzer, the catalyzer cost is lower, and because method provided by the invention can be carried out the olefine saturation hydrogenation of reformed oil under lower temperature, reduced energy consumption, this is reduced with regard to the cost that makes method provided by the invention.
Embodiment
According to method provided by the invention, nickel oxide content is preferably the heavy % of 2-4 in the described catalyzer.The content of cobalt oxide is preferably the heavy % of 0.02-0.5.The ratio that the content of Tungsten oxide 99.999 and/or molybdenum oxide is preferably the heavy % of 4.5-9, described nickel and cobalt total atom number and the total atom number of nickel, cobalt, tungsten and/or molybdenum is preferably 0.4-0.7.
All right in the described catalyzer, and preferably contain a kind of auxiliary agent, described auxiliary agent is selected from one or more in the oxide compound of fluorine or magnesium, phosphorus, and in element, the content of described auxiliary agent is the heavy % of 0.01-8, the heavy % of preferred 0.2-5.
Described alumina supporter is the aluminum oxide that is commonly used for catalyst carrier for hydrgenating.Be preferably gama-alumina, η-aluminum oxide or its mixture.More preferred alumina supporter is gama-alumina or the aluminum oxide be made up of gama-alumina basically.
Catalyzer can carry out prevulcanized before use, makes it to be converted into sulphided state.
Described catalyzer can adopt and soak the technology preparation altogether, and promptly with the common oxide impregnation alumina supporter of the aqueous solution that contains molybdenum and/or tungsten, nickel and cobalt compound, catalyzer is prepared in roasting then.
Described catalyzer preferred manufacturing procedure comprises with containing the aqueous solution of molybdenum and/or tungsten compound and nickel compound and the aqueous solution oxide impregnation alumina supporter of cobalt compound, and the roasting dipping is gone up molybdenum and/or tungsten, the alumina supporter of nickel and cobalt, wherein, described usefulness contains the process of the compound water solution oxide impregnation alumina supporter of cobalt and carries out with separating with the process of the aqueous solution oxide impregnation alumina supporter of tungstenic and/or molybdenum compound and nickel compound, the process of described aqueous solution oxide impregnation alumina supporter with cobalt compound is with after containing the aqueous solution oxide impregnation alumina supporter and roasting of molybdenum and/or tungsten compound and nickel compound, the temperature of carrying out roasting after the described aqueous solution oxide impregnation alumina supporter with cobalt compound is 50-300 ℃, and roasting time was greater than 1 hour.Adopt this method can further improve the low temperature active of catalyzer.
The concrete steps of the preferred manufacturing procedure of described catalyzer are as follows:
(1) with the precursor of aluminum oxide through moulding, drying, have following 500-700 ℃ of roasting 1-6 hour in air or water vapour again, make alumina supporter;
(2) alumina supporter that obtains with compound water solution dipping (1) step that contains molybdenum and/or tungsten and nickel, dry and roasting.The consumption of molybdenum and/or tungsten and nickel compound should make and contain 4 heavy % in the final catalyzer to less than 10 heavy %, the heavy % of preferred 4.5-9 Tungsten oxide 99.999 and/or molybdenum oxide, the heavy % of 1-5, the nickel oxide of the heavy % of preferred 2-4.
(3) product that obtains with the compound water solution of cobalt dipping (2) step, and at 50-300 ℃, preferred 150-250 ℃ of roasting, roasting time is greater than 1 hour, preferred 2-4 hour.Wherein, the consumption of cobalt compound should make in the final catalyzer and contain 0.01-1, the cobalt oxide of the heavy % of preferred 0.02-0.5.
The precursor of described aluminum oxide is selected from the various hydrated aluminum oxides that can generate gama-alumina and/or η-aluminum oxide after the roasting, as pseudo-boehmite, gibbsite etc.The preferred pseudo-boehmite of the precursor of described aluminum oxide or based in the hydrated aluminum oxide of pseudo-boehmite one or more.
Wherein, the dry and roasting that contains behind the aqueous solution oxide impregnation alumina supporter of molybdenum and/or tungsten and nickel compound of described usefulness is carried out under normal condition.As drying temperature can be normal temperature to 200 ℃, and maturing temperature can be 400-600 ℃, and roasting time was preferably 2-5 hour more than 1 hour.
Described dipping can adopt general pickling process or saturated pickling process, preferably adopts saturated pickling process.
It is 150-250 ℃ that described usefulness contains the temperature of carrying out roasting after the compound water solution dipping of cobalt, and roasting time is 2-4 hour.
Described tungsten and/or molybdenum compound are selected from one or more in its water-soluble cpds, preferred ammonium tungstate, ammonium metawolframate and/or ammonium molybdate.Nickel compound can be selected from its water-soluble nitrate, acetate, carbonate, subcarbonate, preferred nickelous nitrate and/or nickel acetate.Cobalt compound can be selected from its water-soluble nitrate, acetate, carbonate, subcarbonate, preferred Xiao Suangu and/or Cobaltous diacetate.
Described Preparation of catalysts method can also comprise the step of flooding described alumina supporter with one or more the aqueous solution that contains in magnesium, phosphorus and the fluorine cpd, described being immersed in before containing molybdenum and/or tungsten compound and nickeliferous compound water solution oxide impregnation alumina supporter carried out, and dipping is after super-dry and roasting.The condition of dry and roasting with flood molybdenum and/or tungsten after drying and roasting condition identical.The consumption of described magnesium, phosphorus and fluorine cpd and the aqueous solution thereof should make in the final catalyzer and contain, in element, and the heavy % of 0.01-8, magnesium, phosphorus and/or the fluorine of the heavy % of preferred 0.2-5.
Magnesium, phosphorus and fluorine cpd are selected from one or more in its water-soluble cpds.Wherein, the preferred magnesium nitrate of magnesium compound, fluorine cpd preferred fluorinated ammonium and/or hydrofluoric acid, one or more in phosphorus compound preferably phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, the primary ammonium phosphate.
According to method provided by the invention, the temperature of described contact is 200-320 ℃, is preferably 220-300 ℃, and the pressure of contact is preferably the 1-10 MPa for being not less than 0.7 MPa, and liquid hourly space velocity is 1-8 hour
-1, be preferably 2-6 hour
-1, hydrogen to oil volume ratio is preferably 50-500 for being not less than 30.
According to method provided by the invention, described reformed oil comprises the product that contains aromatic hydrocarbons and small amounts of olefins that catalytic reforming directly generates, and promptly the reformed oil on the conventional meaning also comprises the aromatic free reforming raffinate oil that obtains after the aromatic hydrocarbons extracting.
The following examples will the present invention will be further described.
Example 1
This example illustrates the preparation of the carrier of method catalyst system therefor provided by the invention.
(solid content is 70 heavy % to take by weighing 5000 gram aluminium hydrate powder A, pseudo-boehmite content 85 heavy %, Shandong Aluminum Plant produces) mix with suitable quantity of water, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters trilobal bar, dried 2 hours for 120 ℃, 600 ℃ of roasts 4 hours are cut into the 2-3 millimeter with the length of the trilobal bar that obtains, make carrier Z
1Carrier Z
1Specific surface, pore volume list in the table 1.Described specific surface and pore volume adopt cryogenic nitrogen absorption BET method to measure (down together).
Example 2
This example illustrates the preparation of the carrier of method catalyst system therefor provided by the invention.
Take by weighing 500 gram examples, 1 described aluminium hydrate powder A (solid content 70 heavy %, pseudo-boehmite content 85 heavy %, Shandong Aluminum Plant produces) and 500 gram aluminium hydrate powder B (solid content 70 heavy %, pseudo-boehmite content 70 heavy %, Chang Ling refinery catalyst plant is produced), thorough mixing adds suitable quantity of water and mixes, and being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters trilobal bar, dried 2 hours for 120 ℃, 600 ℃ of roasts 4 hours are cut into the 2-3 millimeter with the length of the trilobal bar that obtains, make carrier Z
2Carrier Z
2Specific surface, pore volume list in the table 1.
Example 3-5
Following example illustrates the preparation of the carrier that contains auxiliary component of method catalyst system therefor provided by the invention.
Get magnesium nitrate [Mg (NO
3)
26H
2O] 49.0 grams, add deionized water and be made into the 325ml magnesium nitrate aqueous solution, with the magnesium nitrate aqueous solution dipping 500 gram carrier Z that prepare
1, then in 120 ℃ dry 2 hours down, 550 ℃ of following roastings 4 hours make magnesium-containing carrier Z
3
Adopt and use the same method, take by weighing 75 milliliters of Neutral ammonium fluoride (NH4F) 37.5 grams, phosphoric acid (concentration 85.6 heavy %) respectively, add deionized water respectively and be made into 325 milliliters and 330 milliliters of ammonium fluoride aqueous solutions and phosphate aqueous solution, flood 500 gram carrier Z respectively with the ammonium fluoride aqueous solution, the phosphate aqueous solution that prepare
1Then in 120 ℃ dry 2 hours down, 550 ℃ of following roastings 4 hours make fluorine-containing carrier Z
4With phosphorous carrier Z
5Carrier Z
3-Z
5Middle auxiliary agent content (in element) and specific surface, pore volume are listed in the table 1.The content of phosphorus, magnesium, fluorine all adopts x-ray fluorescence spectrometry.
Table 1
| Example number | 1 | 2 | 3 | 4 | 5 |
| Bearer number | Z 1 | Z 2 | Z 3 | Z 4 | Z 5 |
| The auxiliary agent kind | / | / | Mg | F | P |
| The heavy % of auxiliary agent content | 0 | 0 | 0.93 | 3.5 | 2.0 |
| Specific surface, rice 2/ gram | 278 | 283 | 275 | 270 | 272 |
| Pore volume, milliliter/gram | 0.40 | 0.45 | 0.38 | 0.37 | 0.38 |
Example 6-12
The preparation of method catalyst system therefor provided by the invention.
(1) takes by weighing quantitative nickelous nitrate [Ni (NO respectively
3)
26H
2O] and ammonium molybdate is [(NH4)
6Mo
7O
244H
2O] or ammonium metatungstate aqueous solution (be called for short AMT solution, concentration is 77.6 gram WO
3/ 100 ml solns), add deionized water after the mixing, be made into 96 milliliters of aqueous solution that contain nickelous nitrate and ammonium molybdate or ammonium metawolframate.Respectively with the above-mentioned solution impregnation for preparing 150 gram carrier Z
1-Z
54 hours, 120 ℃ of dryings 2 hours, 450 ℃ of roastings 4 hours.Used each material consumption is listed in the table 2.
(2) take by weighing quantitative Xiao Suangu [Co (NO respectively
3)
26H
2O] add deionized water, be made into 94 milliliters of cobalt nitrate aqueous solutions, the product with the cobalt nitrate aqueous solution dipping (1) that is made into obtains respectively 180-230 ℃ of roasting 3 hours, gets method catalyst system therefor C provided by the invention
1-C
7The consumption of Xiao Suangu, maturing temperature and catalyzer C
1-C
7In each component concentration list in the table 2.Wherein the content of cobalt, nickel, molybdenum, tungsten, magnesium, fluorine, phosphorus all adopts x-ray fluorescence spectrometry.
Table 2
| Example number | 6 | 7 | 8 | 9 | 10 | 11 | 12 | |
| The catalyzer numbering | C 1 | C 2 | C 3 | C 4 | C 5 | C 6 | C 7 | |
| The used carrier numbering | Z 1 | Z 1 | Z 2 | Z 3 | Z 4 | Z 5 | Z 1 | |
| Preparation of Catalyst | The nickelous nitrate consumption, gram | 15.60 | 13.25 | 15.90 | 17.80 | 16.50 | 16.60 | 23.40 |
| The ammonium molybdate consumption, gram | 20.50 | |||||||
| The AMT solution usage, milliliter | 16.40 | 13.50 | 13.00 | 16.70 | 16.50 | 18.70 | ||
| The Xiao Suangu consumption, gram | 0.40 | 0.65 | 0.95 | 0.98 | 1.58 | 1.15 | 0.69 | |
| Maturing temperature, ℃ | 180 | 200 | 230 | 200 | 210 | 180 | 230 | |
| The catalyzer compositional analysis | CoO, heavy % | 0.05 | 0.10 | 0.15 | 0.16 | 0.25 | 0.18 | 0.10 |
| NiO, heavy % | 2.40 | 2.05 | 3.25 | 2.79 | 2.50 | 2.57 | 3.51 | |
| WO 3, heavy % | 7.65 | 6.34 | 6.06 | 7.68 | 7.63 | 8.50 | ||
| MoO 3, heavy % | 7.38 | |||||||
| Ni+Co and Ni+Co+W or Mo atomic ratio | 0.50 | 0.51 | 0.46 | 0.60 | 0.53 | 0.53 | 0.56 | |
| Auxiliary agent | Kind | Mg | F | P | ||||
| Content, heavy % | 0.76 | 2.67 | 1.53 | |||||
Comparative Examples 1
The preparation of reference catalyst
Take by weighing 24.25 gram nickelous nitrate [Ni (NO
3)
26H
2O], measure 18.80 milliliters of described AMT solution of example 6-12, the two mixing and adding deionized water are made into 94 milliliters of aqueous solution that contain nickelous nitrate and ammonium metawolframate.With the above-mentioned solution impregnation for preparing 150 gram carrier Z
14 hours, 120 ℃ of dryings 2 hours, 450 ℃ of roasts 4 hours obtain reference catalyst, and it is numbered C
8C
8Middle nickel oxide and tungsten oxide content and nickel are listed in the table 4 with nickel and tungsten atom ratio.
Example 13-19
Following example illustrates method provided by the invention.
Boiling range shown in the his-and-hers watches 3 is that 55-165 ℃ reforming raffinate oil carries out olefine saturation hydrogenation on 100 milliliters of hydrogenation units, and the catalyzer loading amount is 50 milliliters, and catalyst system therefor is respectively catalyzer C
1-C
7, temperature of reaction is 230 ℃, and the hydrogen dividing potential drop is 1.6 MPas, and liquid hourly space velocity is 4 hours
-1, hydrogen to oil volume ratio is 150.Before the reaction at first temperature and the flow velocity at 290 ℃ be in the hydrogen atmosphere of 250 ml/min, with the straight-run spirit that contains dithiocarbonic anhydride 2 heavy % catalyzer was carried out prevulcanized 8 hours, make catalyzer be converted into sulphided state.The bromine valency of reaction product is listed in the table 5.Wherein, the measuring method of bromine valency is referring to " petrochemical complex analytical procedure " (RIPP test method) P172-175, Science Press, 1990.
Comparative Examples 2-4
The saturation hydrogenation method of the reformed oil of existing catalyzer is used in following Comparative Examples explanation.
Method by example 13-19 is carried out olefine saturation hydrogenation to described reforming raffinate oil, and different is that catalyst system therefor is reference catalyst C
8, the industrial trade mark is that catalyzer, the industrial trade mark of CH-17 (Chang Ling refinery catalyst plant product) is the catalyzer of CH-18 (Chang Ling refinery catalyst plant product).The numbering of CH-17, CH-18 catalyzer is followed successively by C
9, C
10, their composition, atoms metal ratio, specific surface and pore volume are listed in the table 4, and the bromine valency of reaction product is listed in the table 6.
Table 3
| The stock oil title | Reforming raffinate oil | Reformed oil |
| d 20 4, gram per centimeter 3 | 0.6578 | 0.7658 |
| The bromine valency, gBr/100g | 14.43 | 3.25 |
| Aromaticity content, heavy % | 0.68 | 55.57 |
| Boiling range ℃ initial boiling point 10% 50% 90% is done | 55 67 78 127 165 | 48 79 115 158 181 |
Table 4
| The catalyzer numbering | Specific surface, rice 2/ gram | Pore volume, milliliter/gram | Metal is formed, heavy % | Nickel (cobalt) and nickel (cobalt), tungsten (molybdenum) atomic ratio |
| C 8 | - | - | NiO：3.62 WO 3：8.53 | 0.56 |
| C 9 | 230 | 0.40 | NiO：6.5 MO 3：19.5 K：0.49 | 0.39 |
| C 10 | 174 | 0.31 | CoO：0.05 NiO：2.40 WO 3：20.0 Mg：0.80 | 0.27 |
Table 5
| Example number | 13 | 14 | 13 | 16 | 17 | 18 | 19 |
| The catalyzer numbering | C 1 | C 2 | C 3 | C 4 | C 5 | C 6 | C 7 |
| Reaction bromide bromine valency, gBr/100g | 0.48 | 0.46 | 0.46 | 0.38 | 0.37 | 0.39 | 0.45 |
Table 6
| Example number | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 |
| The catalyzer numbering | C 8 | C 9 | C 10 |
| Reaction bromide bromine valency, gBr/100g | 0.85 | 0.65 | 0.68 |
Example 20-26
Following example illustrates method provided by the invention.
Method by example 13-19 is carried out olefine saturation hydrogenation to described reforming raffinate oil, and different is that temperature of reaction is 250 ℃, and the bromine valency of reaction product is listed in the table 7.
Comparative Examples 5-7
The saturation hydrogenation method of the reformed oil of existing catalyzer is used in following Comparative Examples explanation.
Method by example 20-26 is carried out olefine saturation hydrogenation to described reforming raffinate oil, and different is that catalyst system therefor is respectively reference catalyst C
8, C
9And C
10, the bromine valency of reaction product is listed in the table 8.
Table 7
| Example number | 20 | 21 | 22 | 23 | 24 | 25 | 26 |
| The catalyzer numbering | C 1 | C 2 | C 3 | C 4 | C 5 | C 6 | C 7 |
| Reaction bromide bromine valency, gBr/100g | 0.08 | 0.08 | 0.07 | 0.05 | 0.04 | 0.04 | 0.08 |
Table 8
| Example number | Comparative Examples 5 | Comparative Examples 6 | Comparative Examples 7 |
| The catalyzer numbering | C 8 | C 9 | C 10 |
| Reaction bromide bromine valency, gBr/100g | 0.18 | 0.09 | 0.08 |
Example 27-33
Following example illustrates method provided by the invention.
Boiling range shown in the his-and-hers watches 3 is that 48-181 ℃ reformed oil carries out olefine saturation hydrogenation on 100 milliliters of hydrogenation units, and the catalyzer loading amount is 50 milliliters, and catalyst system therefor is respectively catalyzer C
1-C
7, temperature of reaction is 270 ℃, and the hydrogen dividing potential drop is 1.0 MPas, and liquid hourly space velocity is 4 hours-1, and hydrogen to oil volume ratio is 100.Before the reaction at first temperature and the flow velocity at 290 ℃ be in the hydrogen atmosphere of 250 ml/min, with the straight-run spirit that contains dithiocarbonic anhydride 2 heavy % catalyzer was carried out prevulcanized 8 hours, make catalyzer be converted into sulphided state.The bromine valency and the aromaticity content of reaction product are listed in the table 9.Wherein, the measuring method of aromaticity content is referring to ASTMD1319-95a.
Comparative Examples 8-10
The olefine saturation hydrogenation method of the reformed oil of existing catalyzer is used in following Comparative Examples explanation.
Method by example 27-33 is carried out olefine saturation hydrogenation to described reformed oil, and different is that catalyst system therefor is respectively reference catalyst C
8, C
9And C
10, the bromine valency and the aromaticity content of reaction product are listed in the table 10.
Table 9
| Example number | 27 | 28 | 29 | 30 | 31 | 32 | 33 |
| The catalyzer numbering | C 1 | C 2 | C 3 | C 4 | C 5 | C 6 | C 7 |
| Reaction bromide bromine valency, gBr/100g | 0.05 | 0.05 | 0.04 | 0.04 | 0.03 | 0.04 | 0.06 |
| Aromaticity content, heavy % | 55.34 | 55.36 | 55.56 | 55.12 | 55.05 | 55.13 | 55.46 |
Table 10
| Example number | Comparative Examples 8 | Comparative Examples 9 | Comparative Examples 10 |
| The catalyzer numbering | C 8 | C 9 | C 10 |
| Reaction bromide bromine valency, gBr/100g | 0.08 | 0.05 | 0.04 |
| Aromaticity content, heavy % | 53.65 | 53.16 | 52.89 |
Claims (10)
1. reformed oil olefine saturation hydrogenation method, this method are included in a kind of catalyzer and exist down, and reformed oil is contacted with hydrogen, it is characterized in that, the temperature of contact is 200-320 ℃, and the pressure of contact is for being not less than 0.7 MPa, and liquid hourly space velocity is 1-8 hour
-1, hydrogen to oil volume ratio is for being not less than 30; Described catalyzer contains Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide that loads on the alumina supporter, with the catalyzer is benchmark, the content of described Tungsten oxide 99.999 and/or molybdenum oxide is that 4 heavy % are to weighing % less than 10, the content of nickel oxide is the heavy % of 1-5, the content of cobalt oxide is the heavy % of 0.01-1, and nickel and cobalt total atom number are 0.3-0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum.
2. method according to claim 1 is characterized in that, nickel oxide content is the heavy % of 2-4 in the described catalyzer, and the content of cobalt oxide is the heavy % of 0.02-0.5.The content of Tungsten oxide 99.999 and/or molybdenum oxide is the heavy % of 4.5-9, and described nickel and cobalt total atom number are preferably 0.4-0.7 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum.
3. method according to claim 1 and 2 is characterized in that, also contains a kind of auxiliary agent in the described catalyzer, and described auxiliary agent is selected from one or more in the oxide compound of fluorine or magnesium, phosphorus, and in element, the content of described auxiliary agent is the heavy % of 0.01-8.
4. method according to claim 3 is characterized in that, the content of described auxiliary agent is the heavy % of 0.2-5.
5. method according to claim 1 is characterized in that described aluminum oxide is gama-alumina or the aluminum oxide be made up of gama-alumina basically.
6. method according to claim 1, it is characterized in that, described catalyzer is the catalyzer that adopts following method preparation, this preparation method comprises with containing the aqueous solution of molybdenum and/or tungsten compound and nickel compound and the aqueous solution oxide impregnation alumina supporter of cobalt compound, and the roasting dipping is gone up molybdenum and/or tungsten, the alumina supporter of nickel and cobalt, wherein, described usefulness contains the process of the compound water solution oxide impregnation alumina supporter of cobalt and carries out with separating with the process of the aqueous solution oxide impregnation alumina supporter of tungstenic and/or molybdenum compound and nickel compound, the process of described aqueous solution oxide impregnation alumina supporter with cobalt compound is with after containing the aqueous solution oxide impregnation alumina supporter and roasting of molybdenum and/or tungsten compound and nickel compound, the temperature of carrying out roasting after the described aqueous solution oxide impregnation alumina supporter with cobalt compound is 50-300 ℃, and roasting time was greater than 1 hour.
7. method according to claim 6 is characterized in that, it is 150-250 ℃ that described usefulness contains the temperature of carrying out roasting after the compound water solution dipping of cobalt, and roasting time is 2～4 hours.
8. method according to claim 6, it is characterized in that, described Preparation of catalysts method can also comprise the step of flooding described alumina supporter with one or more the aqueous solution that contains in magnesium, phosphorus and the fluorine cpd, described being immersed in before containing molybdenum and/or tungsten compound and nickeliferous compound water solution oxide impregnation alumina supporter carried out, dipping after drying and roasting.
9. method according to claim 1 is characterized in that, the temperature of described contact is 220-300 ℃, and the pressure of contact is the 1-10 MPa, and liquid hourly space velocity is 2-6 hour
-1, hydrogen to oil volume ratio is 50-500.
10. method according to claim 1 is characterized in that described reformed oil comprises reforming raffinate oil.
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| CN101376825B (en) * | 2007-08-27 | 2011-11-30 | 中国石油化工股份有限公司 | Hydrotreating process for hydrocarbon oil containing acid |
| CN101376831B (en) * | 2007-08-27 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenation method for hydrocarbon oil containing acid |
| CN101816948B (en) * | 2009-02-27 | 2012-02-29 | 中国石油化工股份有限公司 | Catalytic desulfurization and denitrification catalyst and application thereof |
| CN102399589B (en) * | 2010-09-16 | 2014-04-30 | 中国石油化工股份有限公司 | Method for reducing content of olefin in reformate |
| CN104014337B (en) * | 2014-06-10 | 2017-02-01 | 中国科学院山西煤炭化学研究所 | Catalyst for selective hydrogenation and olefin removal of reformed generated oil as well as preparation method and application |
| CN105669347B (en) * | 2015-12-31 | 2017-11-07 | 浙江工业大学 | A kind of method for reducing linear alkylbenzene (LAB) unsaturated hydrocarbons content |
| CN108636399A (en) * | 2018-04-27 | 2018-10-12 | 中国科学院山西煤炭化学研究所 | The non-precious metal catalyst and its preparation method of reformed oil selective hydrogenation and olefin hydrocarbon removal and application |
| CN109439364B (en) * | 2018-10-31 | 2021-04-16 | 谷育英 | Unsaturated C5Distillate hydrogenation process |
| CN109433220B (en) * | 2018-10-31 | 2021-04-16 | 谷育英 | Nickel-based saturated hydrogenation catalyst and preparation method thereof |
| CN109439365B (en) * | 2018-10-31 | 2021-04-20 | 谷育英 | C4Process for hydrogenating unsaturated hydrocarbons |
| CN109679685B (en) * | 2018-10-31 | 2021-04-16 | 谷育英 | C5Distillate saturation hydrogenation method |
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