CN103191763A - Catalyst composition for producing vinyl chloride, as well as preparation method and application thereof - Google Patents
Catalyst composition for producing vinyl chloride, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst composition for producing vinyl chloride, belonging to the field of production of polyvinyl chloride. The catalyst composition comprises 3-6 parts by weight of mercury chloride, 0.5-4.5 parts by weight of rare earth chloride, 0.5-2.5 parts by weight of copper chloride and/or cuprous chloride and 0.1-1 part by weight of inorganic dispersant. The catalyst composition disclosed by the invention improves the stability of a catalyst by optimizing the formula of the catalyst composition; and by adding a second dispersant, the dispersion uniformity of active components on the surface of a carrier is improved, the content of the mercury chloride can be greatly reduced without reducing the activity and stability of the catalyst, and the production demands can be well met.
Description
Technical field
The present invention relates to the Production of PVC field, particularly a kind ofly generate the low content mercuric chleride catalyst that the vinyl chloride process is used for acetylene and hydrogen chloride synthetic reaction.
Background technology
(Polyvinyl chloride polymer PVC), is the thermoplastic resin that is polymerized under the initator effect by vinyl chloride to polyvinyl chloride, and it has become a kind of indispensable material feedstock owing to have good physicochemical property.Production of PVC technology mainly contains oil ethylene process and carbide acetylene method.The resources characteristic of the rich coal of China, oil-poor, weak breath makes carbide acetylene method become the main flow technology of China's Production of PVC.
Carbide acetylene method is made vinyl chloride by catalyst acetylene and hydrogen chloride generation addition reaction earlier, generates polyvinyl chloride by chloroethylene polymerization again.Catalyst for the production of vinyl chloride is main active component with mercury chloride, active component is loaded on by infusion process on the carriers such as active carbon and makes catalyst.The mercury chloride mass content is at 10-13% in industrial this class catalyst that generally uses.
At present, above-mentioned catalyst has reactivity height, characteristics such as selective good, loss amount is big but such catalyst mercury chloride content height, mercury chloride distil, and the mercury chloride above 50% in the catalyst will be lost to the subsequent production system, thereby can cause bigger mercury pollution.
Summary of the invention
In order to solve prior art problems, the embodiment of the invention provides a kind of carbon monoxide-olefin polymeric for the production of vinyl chloride and preparation method thereof, has used.Described technical scheme is as follows:
On the one hand, provide a kind of carbon monoxide-olefin polymeric for the production of vinyl chloride, having comprised: mercury chloride 3-6 weight portion, rare earth-iron-boron 0.5-4.5 weight portion, copper chloride and/or stannous chloride 0.5-2.5 weight portion, inorganic dispersant 0.1-1 weight portion.
Preferably, described carbon monoxide-olefin polymeric comprises:
Mercury chloride 5.5-6 weight portion, rare earth-iron-boron 1-2 weight portion, copper chloride and/or stannous chloride 0.5-1 weight portion, inorganic dispersant 0.1-0.2 weight portion.
Preferably, described carbon monoxide-olefin polymeric comprises:
Mercury chloride 3.0-4.5 weight portion, rare earth-iron-boron 3-4.5 weight portion, copper chloride and/or stannous chloride 2.0-2.5 weight portion, inorganic dispersant 0.5-1 weight portion.
Preferably, described rare earth-iron-boron is a kind of light rare earth chloride or the muriatic mixture of more than one light rare earths.
Preferably, described inorganic dispersant is one or more combinations in sodium metasilicate, sodium phosphate trimer, calgon, the sodium pyrophosphate.
On the other hand, provide a kind of Preparation of catalysts method for the production of vinyl chloride, described preparation method comprises:
Take by weighing raw material by following percentage by weight: the described carbon monoxide-olefin polymeric 10-13% of claim 1, catalyst carrier 87-90%;
The preparation maceration extract: described carbon monoxide-olefin polymeric is soluble in water, and the mass concentration of making described carbon monoxide-olefin polymeric is the maceration extract of 10-20%;
Impregnated carrier: described catalyst carrier was put into described maceration extract Jin stain more than 24 hours, described Jin stain liquid temp is below 80 ℃, in the dipping process described maceration extract is stirred, mixing speed is 0.5-5 commentaries on classics/min, preceding 6 hours, stirred 5min in per 1 hour, per 2 hours of time in later stage was stirred 5min.
Obtain catalyst: after having flooded, the above-mentioned maceration extract that contains catalyst carrier is carried out Separation of Solid and Liquid, isolated solid phase is carried out drying, get catalyst.
Preferably, described catalyst carrier is modified activated carbon, and the specific area of described modified activated carbon is 750-1300m
2/ g, mechanical strength are greater than 95%.
Particularly, described modified activated carbon makes by following method:
Active carbon is put into strong acid soaked 2-6 hour, filter the active carbon after the pickling:
The pH value of the active carbon after the described pickling is adjusted to neutrality;
Soaked active carbon 1-4 hour that above-mentioned steps obtains with oxidation class strong acid then, isolated by filtration, oven dry get modified activated carbon.
Preferably, described strong acid is one or more combinations in phosphoric acid, sulfuric acid, the hydrochloric acid;
Described acid with strong oxidizing property is one or more combinations in nitric acid, the concentrated sulfuric acid, the perchloric acid.
Have on the one hand, provide above-mentioned catalyst to use in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The acetylene air speed is at 15-35m
3Acetylene/(m
3Catalyst h), reaction temperature 110-180 ℃, hydrogen chloride gas is than the excessive 3-10% of acetylene gas in the unstripped gas.
The beneficial effect that the technical scheme that the embodiment of the invention provides is brought is:
By optimizing the catalyst combination composition formula, improved the stability of catalyst; By the adding dispersion aids, improved the dispersing uniformity of active constituent at carrier surface, guaranteed that when reducing mercury chloride content significantly activity of such catalysts and stability do not reduce, the fine demand that has satisfied production.
The specific embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, embodiment of the present invention is described further in detail below in conjunction with accompanying drawing.
Raw material in the embodiment of the invention is commercial product, the coal charcoal processing of the preferred commercially available diameter 2-4mm specification of wherein said active carbon or unformed coconut husk charcoal, 4-8 order 〉=98%.
Embodiment 1
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 3-6kg, rare earth-iron-boron 0.5-4.5kg, copper chloride and/or stannous chloride 0.5-2.5kg, inorganic dispersant 0.1-1kg, said components is mixed obtain carbon monoxide-olefin polymeric.
Preferably, described rare earth-iron-boron is a kind of light rare earth chloride or the muriatic mixture of more than one light rare earths.
Preferably, described inorganic dispersant is silicates and/or alkali metal phosphate class dispersant, as one or more combinations in sodium metasilicate, sodium phosphate trimer, calgon, the sodium pyrophosphate.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing raw material by following percentage by weight, carbon monoxide-olefin polymeric 10-13%, catalyst carrier 87-90% in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the suitable quantity of water, makes maceration extract, and the mass concentration of carbon monoxide-olefin polymeric described in the described maceration extract is 10-20%;
Impregnated carrier: described maceration extract is put into the dipping still, the catalyst carrier that takes by weighing in the abovementioned steps was put into described maceration extract Jin stain more than 24 hours, control the temperature of described dipping still, make described Jin stain liquid temp below 80 ℃, in the dipping process described maceration extract is stirred, mixing speed is 0.5-5 commentaries on classics/min, preceding 6 hours, stirred 5min in per 1 hour, per 2 hours of time in later stage was stirred 5min.
Obtain catalyst: after dipping is finished, the above-mentioned maceration extract that contains catalyst carrier is carried out Separation of Solid and Liquid, isolated solid phase is carried out drying, get catalyst.
Preferably, described catalyst carrier is modified activated carbon, and more preferably the specific area of described modified activated carbon is 750-1300m
2/ g, mechanical strength are greater than 95%.
The modified product of described active carbon is by following method system:
Active carbon is put into strong acid soaked 2-6 hour, filter the active carbon after the pickling;
The pH value of the active carbon after the described pickling is adjusted to neutrality;
Soaked active carbon 1-4 hour that above-mentioned steps obtains with oxidation class strong acid then, get required active carbon.
Described strong acid is one or more combinations in the strong acid such as phosphoric acid, sulfuric acid, hydrochloric acid;
Described acid with strong oxidizing property is one or more combinations in the acid with strong oxidizing property such as nitric acid, the concentrated sulfuric acid, perchloric acid.
By catalyst carrier is carried out modification, increased the activity of such catalysts center, when reducing mercury chloride content significantly, assurance activity of such catalysts and stability do not reduce, the fine demand that has satisfied production.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 15-35m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is than the excessive 3-10% of acetylene gas in the unstripped gas, and reaction temperature is controlled at 110-180 ℃.
The embodiment of the invention provides catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene, the conversion ratio of acetylene 〉=98%, service life 〉=8000 of catalyst hour.
Embodiment 2
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 3kg, lanthanum chloride 0.5kg, copper chloride 0.5kg, sodium metasilicate 0.1kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 4.1kg, active carbon 36.9kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 36.9kg water, makes maceration extract;
Active carbon is carried out modification to be handled:
The active carbon that above-mentioned steps is taken by weighing is put into an amount of phosphoric acid and was soaked 6 hours, filter the active carbon after the pickling:
The pH value of the active carbon after the described pickling is adjusted to neutrality;
With nitric acid dousing centrifugal filtration separation after 1 hour, will get modified activated carbon after the solid phase oven dry then.
Impregnated carrier: the maceration extract for preparing is put into the dipping still, the modified activated carbon that obtains in the abovementioned steps is immersed in the described maceration extract Jin stain 26 hours, control the temperature of described dipping still, make described Jin stain liquid temp at 70 ℃, and with gate stirrer described maceration extract is stirred in Jin stain process, mixing speed is 5 commentaries on classics/min, preceding 6 hours, stirred 5min in per 1 hour, per 2 hours of time in later stage was stirred 5min.
Obtain catalyst: after dipping is finished, the above-mentioned maceration extract that contains modified activated carbon is carried out Separation of Solid and Liquid, isolated solid phase was dried by the fire 6 hours down at 110 ℃, get catalyst.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 20m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is excessive 3% than acetylene gas in the unstripped gas, and reaction temperature is controlled at 110 ℃.
Embodiment 3
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 3kg, lanthanum chloride 2.5kg, cerium chloride 2kg, copper chloride 0.5kg, stannous chloride 2kg, sodium phosphate trimer 1kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 11kg, active carbon 73.6kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 55kg water, makes maceration extract;
Active carbon is carried out modification to be handled:
The active carbon that above-mentioned steps is taken by weighing is put into an amount of sulfuric acid and was soaked 2 hours, filter the active carbon after the pickling;
The pH value of the active carbon after the described pickling is adjusted to neutrality;
With concentrated sulfuric acid immersion centrifugal filtration separation after 4 hours, will get modified activated carbon after the solid phase oven dry then.
Impregnated carrier: the maceration extract for preparing is put into the dipping still, the modified activated carbon that obtains in the abovementioned steps is immersed in the described maceration extract Jin stain 32 hours, control the temperature of described dipping still, make described Jin stain liquid temp at 60 ℃, and with gate stirrer described maceration extract is stirred in Jin stain process, mixing speed is 2 commentaries on classics/min, preceding 6 hours, stirred 5min in per 1 hour, per 2 hours of time in later stage was stirred 5min.
Obtain catalyst: after dipping is finished, the above-mentioned maceration extract that contains modified activated carbon is carried out Separation of Solid and Liquid, isolated solid phase was dried by the fire 8 hours down at 100 ℃, get catalyst.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 20m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is excessive 10% than acetylene gas in the unstripped gas, and reaction temperature is controlled at 180 ℃.
Embodiment 4
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 6kg, cerium chloride 0.5kg, copper chloride 2.5kg, sodium metasilicate 0.5kg, calgon 0.5kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 10kg, active carbon 67kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 50kg water, makes maceration extract;
Active carbon is carried out modification to be handled:
The active carbon that above-mentioned steps is taken by weighing is put into appropriate hydrochloric acid and was soaked 2 hours, filter the active carbon after the pickling;
The pH value of the active carbon after the described pickling is adjusted to neutrality;
With perchloric acid immersion centrifugal filtration separation after 4 hours, will get modified activated carbon after the solid phase oven dry then.
Impregnated carrier: the maceration extract for preparing is put into the dipping still, the modified activated carbon that obtains in the abovementioned steps is immersed in the described maceration extract Jin stain 32 hours, control the temperature of described dipping still, make described Jin stain liquid temp at 60 ℃, and with gate stirrer described maceration extract is stirred in Jin stain process, mixing speed is 1 commentaries on classics/min, preceding 6 hours, stirred 5min in per 1 hour, per 2 hours of time in later stage was stirred 5min.
Obtain catalyst: after dipping is finished, the above-mentioned maceration extract that contains modified activated carbon is carried out Separation of Solid and Liquid, isolated solid phase was dried by the fire 8 hours down at 100 ℃, get catalyst.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 30m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is excessive 8% than acetylene gas in the unstripped gas, and reaction temperature is controlled at 180 ℃.
Embodiment 5
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 6kg, lanthanum chloride 4kg, cerium chloride 0.5kg, copper chloride 0.5kg, sodium pyrophosphate 0.1kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 11kg, active carbon 73.6kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 55kg water, makes maceration extract;
Active carbon is carried out modification to be handled:
The active carbon that above-mentioned steps is taken by weighing is put into appropriate hydrochloric acid and was soaked 2 hours, filter the active carbon after the pickling;
The pH value of the active carbon after the described pickling is adjusted to neutrality;
With perchloric acid immersion centrifugal filtration separation after 4 hours, will get modified activated carbon after the solid phase oven dry then.
Impregnated carrier: the maceration extract for preparing is put into the dipping still, the modified activated carbon that obtains in the abovementioned steps is immersed in the described maceration extract Jin stain 32 hours, control the temperature of described dipping still, make described Jin stain liquid temp at 60 ℃, and with anchor agitator described maceration extract is stirred in Jin stain process, mixing speed is 1 commentaries on classics/min, preceding 6 hours, stirred 5min in per 1 hour, per 2 hours of time in later stage was stirred 5min.
Obtain catalyst: after dipping is finished, the above-mentioned maceration extract that contains modified activated carbon is carried out Separation of Solid and Liquid, isolated solid phase was dried by the fire 8 hours down at 100 ℃, get catalyst.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 30m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is excessive 7% than acetylene gas in the unstripped gas, and reaction temperature is controlled at 180 ℃.
Embodiment 6
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 5.5kg, lanthanum chloride 1kg, cerium chloride 1kg, copper chloride 0.5kg, stannous chloride 0.5kg, sodium metasilicate 0.1kg, sodium pyrophosphate 0.1kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 8.7kg, active carbon 58.2kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 43.5kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 5.
Embodiment 7
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 6kg, lanthanum chloride 1kg, stannous chloride 0.5kg, sodium metasilicate 0.1kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 7.6kg, active carbon 50.9kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 38kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 5.
Embodiment 8
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 6kg, lanthanum chloride 2kg, copper chloride 0.5kg, stannous chloride 0.5kg, sodium metasilicate 0.2kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 9.2kg, active carbon 61.6kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 46kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 5.
Embodiment 9
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 3kg, lanthanum chloride 3kg, stannous chloride 2kg, sodium metasilicate 0.5kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 8.5kg, active carbon 56.9kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 42.5kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 20m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is excessive 7% than acetylene gas in the unstripped gas, and reaction temperature is controlled at 180 ℃.
Embodiment 10
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 3kg, lanthanum chloride 4.5kg, copper chloride 0.5kg, stannous chloride 2kg, sodium metasilicate 1kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 11kg, active carbon 73.6kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 55kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 9.
Embodiment 11
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 4.5kg, lanthanum chloride 3kg, copper chloride 0.5kg, stannous chloride 2kg, sodium metasilicate 0.5kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 10kg, active carbon 67kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 50kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 9.
Embodiment 12
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 4.5kg, lanthanum chloride 4.5kg, copper chloride 0.5kg, stannous chloride 2kg, sodium metasilicate 0.5kg, sodium pyrophosphate 0.5kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 12.5kg, active carbon 83.7kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 62.5kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 25m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is excessive 7% than acetylene gas in the unstripped gas, and reaction temperature is controlled at 180 ℃.
Embodiment 13
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 4.5kg, lanthanum chloride 2kg, copper chloride 1kg, sodium pyrophosphate 0.3kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 7.8kg, active carbon 52.2kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 39kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 12.
Embodiment 14
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 5.5kg, lanthanum chloride 3kg, copper chloride 2kg, sodium pyrophosphate 0.5kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 11kg, active carbon 73.6kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 55kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 12.
Embodiment 15
(1) for the preparation of the carbon monoxide-olefin polymeric of producing vinyl chloride:
Take by weighing mercury chloride 5.5kg, lanthanum chloride 2kg, copper chloride 1kg, sodium pyrophosphate 0.3kg, above-mentioned raw materials is mixed obtain carbon monoxide-olefin polymeric.
(2) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: take by weighing carbon monoxide-olefin polymeric 8.8kg, active carbon 67.7kg in the step (1);
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 44kg water, makes maceration extract;
Active carbon is carried out modification to be handled: with embodiment 5.
Impregnated carrier: with embodiment 5.
Obtain catalyst: with embodiment 5.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
With embodiment 12.
Comparative Examples
(1) for the preparation of the catalyst of producing vinyl chloride:
Prepare raw material: mercury chloride 11kg, active carbon 3.6kg;
The preparation maceration extract: the carbon monoxide-olefin polymeric that above-mentioned steps is taken by weighing is dissolved in the 55kg water, makes maceration extract;
Impregnated carrier: the maceration extract for preparing is put into the dipping still, active carbon is immersed in the described maceration extract Jin stain 32 hours, control the temperature of described dipping still, make described Jin stain liquid temp at 60 ℃.
Obtain catalyst: after dipping is finished, the above-mentioned maceration extract that contains active carbon is carried out Separation of Solid and Liquid, isolated solid phase was dried by the fire 8 hours down at 100 ℃, get catalyst.
(3) application of catalyst in acetylene and hydrogen chloride gas synthesizing chloroethylene process, its application conditions comprises:
The catalyst of 3.2 tons of preparations of filling feeds unstripped gas in the converter of 2.4 rice diameters, and wherein the acetylene air speed is at 30m
3Acetylene/(m
3Catalyst h), hydrogen chloride gas is excessive 7% than acetylene gas in the unstripped gas, and reaction temperature is controlled at 180 ℃.
The effect of embodiment of the invention 2-15 and Comparative Examples catalyzing acetylene and hydrogen chloride gas synthesizing chloroethylene sees Table 1.
Table 1 embodiment of the invention 2-15 and Comparative Examples are in acetylene and the hydrogen chloride gas synthesizing chloroethylene process
Catalytic action
| Embodiment | 1000 hours second | 2000 hours second | 4000 hours acetylene | 6000 hours acetylene | 8000 hours second |
| ? | The alkynes average conversion | The alkynes average conversion | Average conversion | Average conversion | The alkynes average conversion |
| 2 | 98.6％ | 98.6％ | 98.4％ | 98.2％ | 98.0％ |
| 3 | 98.4％ | 98.4％ | 98.3％ | 98.2％ | 98.0％ |
| 4 | 98.6％ | 98.6％ | 98.4％ | 98.0％ | 98.0％ |
| 5 | 98.5％ | 98.5％ | 98.3％ | 98.2％ | 98.1％ |
| 6 | 99.5％ | 99.5％ | 99.3％ | 99.0％ | 98.6％ |
| 7 | 99.6％ | 99.6％ | 99.4％ | 99.2％ | 98.8％ |
| 8 | 99.4％ | 99.4％ | 99.2％ | 99.1％ | 98.9％ |
| 9 | 99.1％ | 99.1％ | 99.0％ | 98.7％ | 98.5％ |
| 10 | 99.3％ | 99.3％ | 99.1％ | 98.7％ | 98.5％ |
| 11 | 99.5％ | 99.2％ | 99.0％ | 98.8％ | 98.7％ |
| 12 | 99.4％ | 99.4％ | 99.2％ | 98.9％ | 98.6％ |
| 13 | 99.3％ | 99.3％ | 99.1％ | 98.7％ | 98.3％ |
| 14 | 99.2％ | 99.1％ | 99.0％ | 98.6％ | 98.4％ |
| 15 | 99.6％ | 99.6％ | 99.2％ | 98.9％ | 98.5％ |
| Comparative Examples | 98.2％ | 98.2％ | 90.2％ | 80.1％ | 76.3％ |
As shown in Table 1, the catalyst that the embodiment of the invention provides is in catalyzing acetylene and hydrogen chloride gas synthesizing chloroethylene technology, and the conversion ratio of acetylene can reach more than 98%, and the service life of catalyst was greater than 8000 hours.Wherein embodiment 6-8 is at tolerance 30m
3Acetylene/(m
3Catalyst h) under, still can reach more than 98.5% at the conversion ratio of catalyst work acetylene after 8000 hours; The mercury chloride of embodiment 9-12 in the catalyst activity component dropped to for 4.5 weight portion following times, and the conversion ratio of catalyst work acetylene after 8000 hours still can reach more than 98.5%.And the catalyst that Comparative Examples provides is along with the increase of working time, and the conversion ratio of acetylene is more and more lower.
The invention described above embodiment sequence number does not represent the quality of embodiment just to description.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the carbon monoxide-olefin polymeric for the production of vinyl chloride comprises: mercury chloride 3-6 weight portion, rare earth-iron-boron 0.5-4.5 weight portion, copper chloride and/or stannous chloride 0.5-2.5 weight portion, inorganic dispersant 0.1-1 weight portion.
2. the carbon monoxide-olefin polymeric for the production of vinyl chloride as claimed in claim 1 is characterized in that, described carbon monoxide-olefin polymeric comprises:
Mercury chloride 5.5-6 weight portion, rare earth-iron-boron 1-2 weight portion, copper chloride and/or stannous chloride 0.5-1 weight portion, inorganic dispersant 0.1-0.2 weight portion.
3. the carbon monoxide-olefin polymeric for the production of vinyl chloride as claimed in claim 1 is characterized in that, described carbon monoxide-olefin polymeric comprises:
Mercury chloride 3.0-4.5 weight portion, rare earth-iron-boron 3-4.5 weight portion, copper chloride and/or stannous chloride 2.0-2.5 weight portion, inorganic dispersant 0.5-1 weight portion.
4. as the described carbon monoxide-olefin polymeric for the production of vinyl chloride of each claim of claim 1-3, it is characterized in that described rare earth-iron-boron is a kind of light rare earth chloride or the muriatic mixture of more than one light rare earths.
5. as the described carbon monoxide-olefin polymeric for the production of vinyl chloride of each claim of claim 1-3, it is characterized in that described inorganic dispersant is one or more combinations in sodium metasilicate, sodium phosphate trimer, calgon, the sodium pyrophosphate.
6. Preparation of catalysts method for the production of vinyl chloride is characterized in that described preparation method comprises:
Take by weighing raw material by following percentage by weight: the described carbon monoxide-olefin polymeric 10-13% of claim 1, catalyst carrier 87-90%;
The preparation maceration extract: described carbon monoxide-olefin polymeric is soluble in water, and the mass concentration of making described carbon monoxide-olefin polymeric is the maceration extract of 10-20%;
Impregnated carrier: described catalyst carrier was put into described maceration extract Jin stain more than 24 hours, described Jin stain liquid temp is below 80 ℃, in the dipping process described maceration extract is stirred, mixing speed is 0.5-5 commentaries on classics/min, preceding 6 hours, stirred 5min in per 1 hour, per 2 hours of time in later stage was stirred 5min.
Obtain catalyst: after having flooded, the above-mentioned maceration extract that contains catalyst carrier is carried out Separation of Solid and Liquid, isolated solid phase is carried out drying, get catalyst.
7. the Preparation of catalysts method for the production of vinyl chloride as claimed in claim 6 is characterized in that, described catalyst carrier is modified activated carbon, and the specific area of described modified activated carbon is 750-1300m
2/ g, mechanical strength are greater than 95%.
8. the Preparation of catalysts method for the production of vinyl chloride as claimed in claim 7 is characterized in that,
Described modified activated carbon makes by following method:
Active carbon is put into strong acid soaked 2-6 hour, filter the active carbon after the pickling;
The pH value of the active carbon after the described pickling is adjusted to neutrality;
Soaked active carbon 1-4 hour that above-mentioned steps obtains with oxidation class strong acid then, isolated by filtration, oven dry get modified activated carbon.
9. the Preparation of catalysts method for the production of vinyl chloride as claimed in claim 7 is characterized in that,
Described strong acid is one or more combinations in phosphoric acid, sulfuric acid, the hydrochloric acid;
Described acid with strong oxidizing property is one or more combinations in nitric acid, the concentrated sulfuric acid, the perchloric acid.
10. the catalyst of each claim preparation of claim 6-9 is used in acetylene and hydrogen chloride gas synthesizing chloroethylene process, it is characterized in that its application conditions comprises:
The acetylene air speed is at 15-35m
3Acetylene/(m
3Catalyst h), reaction temperature 110-180 ℃, hydrogen chloride gas is than the excessive 3-10% of acetylene gas in the unstripped gas.
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| CN105289603A (en) * | 2014-12-02 | 2016-02-03 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Method for preparing high-dispersibility gold-loading catalyst |
| CN105618080A (en) * | 2016-01-30 | 2016-06-01 | 凯姆德（北京）能源环境科技有限公司 | Ozone catalytic oxidation catalyst for treating reverse osmosis concentrated water and preparation method of catalyst |
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