CN101947465A - Mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof - Google Patents
Mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof Download PDFInfo
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- CN101947465A CN101947465A CN 201010272612 CN201010272612A CN101947465A CN 101947465 A CN101947465 A CN 101947465A CN 201010272612 CN201010272612 CN 201010272612 CN 201010272612 A CN201010272612 A CN 201010272612A CN 101947465 A CN101947465 A CN 101947465A
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Abstract
The invention discloses a mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof and belongs to the technical field of a catalyst for the acetylene hydrochlorination and a preparation technique and a reaction process thereof. The catalyst comprises a noble metal element which accounts for 0.05 to 0.5 weight percent of the total weight of the catalyst, a common metal element which accounts for 0.1 to 5 weight percent of the total weight of the catalyst, and a carrier, wherein the noble metal element and the noble metal element exist in the form of metallic compounds. The noble metal element content of the catalyst is reduced greatly, the loading amount of a cocatalyst metallic element is also low, and the cost of the catalyst is reduced greatly; and the catalyst can replace the highly toxic mercury catalyst and is applied to the industrial production of the acetylene hydrochlorination.
Description
Technical field
The invention belongs to acetylene hydrochlorination with catalyst and technology of preparing and reaction process technical field, particularly be used for the low precious metal content catalyst without mercury and the application thereof of acetylene hydrochlorination reaction.
Background technology
Polyvinyl chloride is stable etc. with its excellent physical property, chemical property, be purposes one of plastics the most widely in the world, also be the plastic made of synthetic resin of China's output and consumption figure maximum, be mainly used in every field such as building materials, electric equipment products, furniture, medicine.The raw material monomer of polyvinyl chloride is a VCM, though most of country adopts the synthesis material of ethene as VCM in the world wide at present, but because the national conditions of the few oil of the many coals of China and the technology economy advantage of coal system acetylene method, mainly still adopt calcium carbide-acetylene process route to prepare VCM, mercury chloride/active carbon catalyst that this process adopts utilizes fixed bed reactors to synthesize.Because of the restriction of being conducted heat, fixed bed reactors separate unit production capacity is little, hot(test)-spot temperature is high, and what catalyst adopted simultaneously is mercury catalyst, makes long-term use cause serious environmental to pollute.At the industry Situation of the present carbide preparing chloroethylene of China, realize green sustainable development in order to make the polyethylene industry, imperative for the research and development of catalyst without mercury.
Because the mercury catalyst serious environment pollution has had some researchs at low-mercury catalyst and catalyst without mercury at present.Nankai University Deng state just waits the people to study the catalyst of common metal chlorides such as stannic chloride as active component, though higher active and selectivity is preferably arranged, its loss of active component is rapid, and catalysqt deactivation is fast, and the commercial Application difficulty is bigger; People such as Britain scholar Hutings have carried out series of studies to single metals of noble metal such as Au, Pd, Pt and the combination between them, they have proved that noble metal has certain catalytic action for acetylene hydrochlorination, Au has advantages of high catalytic activity as catalyst for acetylene hydrochlorination comparatively speaking, and inactivation is slower, but their the catalyst noble metal load proportion of preparation is higher, catalyst activity is low, makes the cost height of commercial Application; People such as south China science and engineering Wang Sheng outstanding person have proposed the Au-Cu/C catalyst, activity and stable is preferably arranged, but its Au content are difficult to be applied to industrial production still than higher.
Summary of the invention
Based on above background, the present invention proposes a kind of low precious metal content catalyst without mercury and application thereof that is used for the acetylene hydrochlorination reaction.
A kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction, it is characterized in that: this catalyst comprises precious metal element, common metal and carrier, described precious metal element accounts for the 0.05wt%～0.5wt% of total catalyst weight, preferred 0.1wt%～0.3wt%; Described common metal accounts for the 0.1wt%～5wt% of total catalyst weight, preferred 0.4wt%～3wt%; Described precious metal element and common metal all exist with the form of metallic compound.
One or more metallic elements among the preferred Au of described precious metal element, Pt, Rh, Ru, Ir, the Pd.
One or more metallic elements in described common metal preferably copper, zinc, potassium, barium, nickel, bismuth, calcium, lithium and the rare earth metal.
Described form with metallic compound exists preferably and exists with one or more forms in metal chloride, metal phosphate or the metal sulfate.
The preferred active carbon of described carrier, silica gel, molecular sieve, CNT, TiO
2, one or more the combination in the aluminium oxide.
A kind of application that is used for the low precious metal content catalyst without mercury of acetylene hydrochlorination reaction is characterized in that: the reaction condition that utilizes described catalyst without mercury to carry out the acetylene hydrochlorination reaction is: reaction temperature is 100～250 ℃, acetylene volume space velocity 20～2000h
-1, pressure 0.01～1MPa.
Described catalyst without mercury can be used for fixed bed, fluid bed, moving bed or integer catalyzer reactor, the form of described fluid bed comprises bubbling bed, turbulent bed, recirculating fluidized bed and Mnltilayered structures fluid bed, and the form of described moving bed comprises axial moving bed, radial flow moving bed and multistage moving bed.
The catalyst granules that is used for fixing bed is 0.5～10mm, the catalyst granules that is used for fluid bed is 0.03～10mm, being used for the movable bed catalyst particle is 1～10mm, the integer catalyzer reactor catalyst is ceramic base or Metal Substrate matrix, aperture size is 0.5～10mm, and the catalyst system therefor shape can adopt sphere, cylindricality, cloverleaf pattern or annular.
Low precious metal content catalyst without mercury of the present invention can adopt equi-volume impregnating or coprecipitation preparation, and equi-volume impregnating relates generally to processing steps such as mother liquor preparation, carrier impregnation, drying and activation, and the preparation method is as follows:
(1) be raw material with precious metal chemical complex and common metal compound, carrier, after determining the quality of preparation catalyst, the percentage composition that accounts for catalyst gross mass to be prepared according to precious metal element, common metal is determined the quality of precious metal chemical complex, common metal compound and carrier and adding solvent;
(2) preparation dipping mother liquor: precious metal chemical complex and common metal compound are dissolved in the deionized water, stir the mixture to whole dissolvings; For precious metal chemical complex that is insoluble to deionized water and common metal compound, behind certain deionized water to be added, drip an amount of concentrated hydrochloric acid as solvent, be stirred to whole dissolvings, the dipping mother liquor that obtains clarifying;
(3) add the catalyst carrier incipient impregnation: in the mother liquor of clarification, add catalyst carrier, make settled solution just flood carrier, liquid-solid mixture is left standstill 2～4h;
(4) oven dry and roasting: will flood the liquid-solid mixture of getting well and dry according to following heating schedule: 20 ℃ at the uniform velocity are warmed up to 100 ℃ through 20～60min, and 100 ℃ at the uniform velocity are warmed up to 130 ℃ through 0.5～2h, at 130 ℃ of constant temperature 4～8h, drop to room temperature then; With the oven dry catalyst at N
2Atmosphere under under 150 ℃～300 ℃ temperature, carry out roasting, roasting time 30～60min;
(5) activation: the catalyst that roasting is good activates in HCl atmosphere, and soak time 10～60min makes low precious metal content catalyst without mercury of the present invention.
In precious metal chemical complex preferable alloy chloride, metal phosphate, metal sulfate or the metal oxide described in the said method one or more, one or more metallic elements among the preferred Au of the precious metal element in the precious metal chemical complex, Pt, Rh, Ru, Ir, the Pd; In described common metal compound preferable alloy chloride, metal phosphate, metal sulfate or the metal oxide one or more, one or more metallic elements in common metal preferably copper, zinc, potassium, barium, nickel, bismuth, calcium, lithium and the rare earth metal in the common metal compound; Described carrier can be selected from active carbon, silica gel, molecular sieve, CNT, TiO
2, one or more the combination in the aluminium oxide.
Said common metal is meant the base metal element among the present invention.When common metal used separately, catalyst activity was very low or almost do not have catalytic activity, but can improve the catalytic activity of precious metal element greatly.The present invention utilizes precious metal element and common metal concerted catalysis acetylene hydrochlorination process and a kind of low precious metal content catalyst without mercury and application thereof that is used for the acetylene hydrochlorination reaction is provided.
Beneficial effect of the present invention is: precious metal element content reduces greatly in the catalyst of the present invention, and the common metal load capacity is also lower, has reduced the cost of catalyst greatly, and the catalyst bullion content that makes is low, and catalytic activity is good, the selectivity height.This catalyst is applied to the acetylene hydrochlorination industrial processes in the hope of replacing the high toxicity mercury catalyst.
The specific embodiment
Embodiment 1:
The Au-Cu-Cl/ silica-gel catalyst, carrier adopts silica gel, and catalyst is by AuCl
3, CuCl
2Form with silica gel, wherein, the amount of Au is 0.05% of a catalyst quality, and the amount of Cu is 2% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 160 ℃ of reaction temperatures, reaction pressure is 0.1MPa.The acetylene initial conversion is 40%, and reaction 4hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Embodiment 2:
Au-Cl-Cu-SO
4/ C catalyst, carrier adopts active carbon, and catalyst is by AuCl
3, CuSO
4Form with active carbon, wherein the amount of Au is 0.1% of a catalyst quality, and the amount of Cu is 2% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 160 ℃ of reaction temperatures, reaction pressure is 0.12MPa.The acetylene initial conversion is 80%, and reaction 9hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Embodiment 3:
The Au-Zn-Cl/C catalyst, carrier adopts active carbon, and catalyst is by AuCl
3, ZnCl
2Form with active carbon, wherein the amount of Au is 0.05% of a catalyst quality, and the amount of Zn is 2% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 160 ℃ of reaction temperatures, reaction pressure is 0.1Mpa.The acetylene initial conversion is 50%, and reaction 6hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 96～99%.
Embodiment 4:
The Au-Bi-Cl/C catalyst, carrier is an active carbon, catalyst is by AuCl
3, BiCl
3Form with active carbon, wherein the amount of Au is 0.05% of a catalyst quality, and the amount of Bi is 2% of a catalyst quality, and carrier adopts active carbon.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 160 ℃ of reaction temperatures, reaction pressure 0.15Mpa.The acetylene initial conversion is 75%, and reaction 6hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Embodiment 5:
The Pt-Bi-Cu-Cl/C catalyst, carrier is an active carbon, catalyst is by PtCl
3, BiCl
3, CuCl
2Form wherein with active carbon that the amount of Pt is 0.4% of a catalyst quality, the amount of Bi is 2% of a catalyst quality, and the amount of Cu is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 180 ℃ of reaction temperatures, reaction pressure is 0.13MPa.The acetylene initial conversion is 85%, and reaction 6hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Embodiment 6
The Au-Bi-Li-Cl/C catalyst, carrier adopts active carbon, and catalyst is by AuCl
3, BiCl
3, LiCl and active carbon form, wherein the amount of Au is 0.05% of a catalyst quality, the amount of Bi is 2% of a catalyst quality, the amount of Li is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 160 ℃ of reaction temperatures, reaction pressure is 0.12MPa.The acetylene initial conversion is 76%, and reaction 4hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Implement 7:
Pt-Bi-K-PO
4/ C catalyst, carrier adopts active carbon, and catalyst is by PtCl
3, BiPO
4, KCl and active carbon form, wherein the amount of Pt is 0.2% of a catalyst quality, the amount of Bi is 2% of a catalyst quality, the amount of K is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 160 ℃ of reaction temperatures, reaction pressure 0.2MPa.The acetylene initial conversion is 70%, and reaction 4hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Implement 8:
The Au-Bi-Ni-Cl/C catalyst, carrier adopts active carbon, and catalyst is by AuCl
3, BiCl
3, NiCl
3Form with active carbon, wherein the amount of Au is 0.05% of a catalyst quality, and the amount of Bi is 2% of a catalyst quality, and the amount of Ni is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 170 ℃ of reaction temperatures, reaction pressure is 0.13MPa.The acetylene initial conversion is 75%, and reaction 4hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Implement 9:
The Rh-Bi-Ba-Cl/C catalyst, carrier adopts active carbon, and catalyst is by RhCl
3, BiCl
3, BaCl
2Form with active carbon, wherein the amount of Rh is 0.1% of a catalyst quality, and the amount of Bi is 2% of a catalyst quality, and the amount of Ba is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 160 ℃ of reaction temperatures, reaction pressure is 0.5Mpa.The acetylene initial conversion is 60%, and reaction 4hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Implement 10:
The Ir-Bi-Ca-Cl/C catalyst, carrier is for adopting active carbon, and catalyst is by IrCl
3, BiCl
3, CaCl
2Form with active carbon, wherein the amount of Ir is 0.3% of a catalyst quality, and the amount of Bi is 2% of a catalyst quality, and the amount of Ca is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 170 ℃ of reaction temperatures, reaction pressure is 0.8MPa.The acetylene initial conversion is 65%, and reaction 4hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Embodiment 11:
The Au-Pd-Cl/C catalyst, carrier adopts active carbon, and catalyst is by AuCl
3, PdCl
2Form with active carbon, wherein the amount of Au is 0.1% of a catalyst quality, and Pd is 0.3% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 180 ℃ of reaction temperatures, reaction pressure is 0.12Mpa.The acetylene initial conversion is 70%, and reaction 6hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 97～99%.
Embodiment 12:
The Pt-Ce-Cl/C catalyst, carrier adopts active carbon, and catalyst is by PtCl
2, CeCl
3Form with active carbon, wherein the content of Pt is 0.2% of catalyst quality, and the amount of Ce is 2% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 170 ℃ of reaction temperatures, reaction pressure is 0.3Mpa.The acetylene initial conversion is 60%, and reaction 4hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 95～97%.
Embodiment 13:
The Au-Cu-K-Cl/C catalyst, carrier is an active carbon, catalyst is by AuCl
3, CuCl
2, KCl and active carbon form, wherein Au content is 0.1% of catalyst quality, the amount of Cu is 3% of a catalyst quality, the amount of K is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction in bubbling fluidized bed, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, setting reaction temperature is 170 ℃, and bed temperature remains on below 173 ℃ in the course of reaction, and reaction pressure is 0.12MPa.The acetylene initial conversion is 70%, and reaction 15hr conversion ratio does not descend, and the selectivity of vinyl chloride is 98～99%.
Embodiment 14:
The Pt-Bi-Cu-Cl/C catalyst, carrier is an active carbon, catalyst is by PtCl
2, BiCl
3, CuCl
2Form with active carbon, wherein the amount of Pt is 0.3% of a catalyst quality, and the amount of Bi is 2% of a catalyst quality, and the amount of Cu is 1% of a catalyst quality.
Utilize this catalyst to carry out the acetylene hydrochlorination reaction in bubbling fluidized bed, reaction condition is as follows: reaction gas is according to mol ratio C
2H
2: HCl=1: 1.1, acetylene volume space velocity 400h
-1, set 180 ℃ of reaction temperatures, the course of reaction bed temperature maintains below 184 ℃, and reaction pressure is 0.15MPa.The acetylene initial conversion is 85%, and reaction 20hr conversion ratio does not reduce, and the selectivity of vinyl chloride is 98～99%.
Claims (10)
1. one kind is used for the low precious metal content catalyst without mercury that acetylene hydrochlorination reacts, it is characterized in that: this catalyst comprises precious metal element, common metal and carrier, described precious metal element accounts for the 0.05wt%～0.5wt% of total catalyst weight, described common metal accounts for the 0.1wt%～5wt% of total catalyst weight, and described precious metal element and common metal all exist with the form of metallic compound.
2. a kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction according to claim 1, it is characterized in that: described precious metal element accounts for the 0.1wt%～0.3wt% of total catalyst weight.
3. a kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction according to claim 1, it is characterized in that: described common metal accounts for the 0.4wt%～3wt% of total catalyst weight.
4. a kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction according to claim 1, it is characterized in that: described precious metal element comprises one or more metallic elements among Au, Pt, Rh, Ru, Ir, the Pd.
5. a kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction according to claim 1, it is characterized in that: described common metal comprises one or more metallic elements in copper, zinc, potassium, barium, nickel, bismuth, calcium, lithium and the rare earth metal.
6. a kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction according to claim 1, it is characterized in that: described form with metallic compound exists one or more forms that comprise with in metal chloride, metal phosphate or the metal sulfate to exist.
7. a kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction according to claim 1, it is characterized in that: described carrier is selected from active carbon, silica gel, molecular sieve, CNT, TiO
2, one or more the combination in the aluminium oxide.
8. application that is used for the low precious metal content catalyst without mercury of acetylene hydrochlorination reaction, it is characterized in that: the reaction condition that utilizes the described catalyst without mercury of any one claim of claim 1 to 7 to carry out the acetylene hydrochlorination reaction is: reaction temperature is 100～250 ℃, acetylene volume space velocity 20～2000h
-1, pressure 0.01～1MPa.
9. a kind of application that is used for the low precious metal content catalyst without mercury of acetylene hydrochlorination reaction according to claim 8, it is characterized in that: described catalyst without mercury is applicable to fixed bed, fluid bed, moving bed or integer catalyzer reactor, the form of described fluid bed comprises bubbling bed, turbulent bed, recirculating fluidized bed and Mnltilayered structures fluid bed, and the form of described moving bed comprises axial moving bed, radial flow moving bed and multistage moving bed.
10. a kind of application that is used for the low precious metal content catalyst without mercury of acetylene hydrochlorination reaction according to claim 8, it is characterized in that: the catalyst granules that is used for fixing bed is 0.5～10mm, the catalyst granules that is used for fluid bed is 0.03～10mm, being used for the movable bed catalyst particle is 1～10mm, the integer catalyzer reactor catalyst is ceramic base or Metal Substrate matrix, aperture size is 0.5～10mm, and the catalyst system therefor shape adopts sphere, cylindricality, cloverleaf pattern or annular.
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