CN102145303B - Environmental-friendly mercuric chloride metal catalyst and preparation method thereof - Google Patents
Environmental-friendly mercuric chloride metal catalyst and preparation method thereof Download PDFInfo
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- CN102145303B CN102145303B CN201110034442A CN201110034442A CN102145303B CN 102145303 B CN102145303 B CN 102145303B CN 201110034442 A CN201110034442 A CN 201110034442A CN 201110034442 A CN201110034442 A CN 201110034442A CN 102145303 B CN102145303 B CN 102145303B
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Abstract
The invention discloses an environmental-friendly mercuric chloride metal catalyst, which consists of an inhomogeneous mercuric chloride metal catalyst and a polymer coated on the surface of the inhomogeneous mercuric chloride metal catalyst in a film mode. In a reaction of producing vinyl chloride by acetylene hydrochlorination, due to the adoption of the catalyst, on the premise of ensuring the activity of the catalyst and the selectivity of vinyl chloride, the environment and health problems caused by Hg sublimation are reduced. The catalyst has the characteristics of high catalyzing efficiency, low toxicity, mild catalyst release and the like. The invention also discloses a preparation method of the environmental-friendly mercuric chloride metal catalyst. In the preparing process, few parameters need to be controlled. The preparation method has high repeatability and strong controllability and is easy for industrial production.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of environment friendly chlorinated mercury (HgCl
2) metallic catalyst and preparation method thereof.
Background technology
Vinyl chloride is important organic synthesis raw material, and topmost purposes is to produce polyvinyl chloride (PVC).In China, the output of vinyl chloride and sales volume are all at the forefront in the world.At present, the method for industrial production vinyl chloride mainly contains ethylene process and acetylene method.Wherein acetylene method technology is simple, but owing to employing mercury chloride in the technical process is catalyst, mercury chloride has very high toxicity; Poor stability, easily distillation (136.2 ℃ time, the vapour pressure of mercury chloride is 133Pa); Can influence workers'health, also can cause environmental pollution, superseded basically abroad.And in China, because the ethene scarcity of resources, acetylene method still occupies about 80% market.At present, for solving the problem of mercury pollution, people have done a large amount of work, and mainly concentrate on two aspects: alternative HgCl is sought in (1)
2Catalyst; (2) preparation environment-friendly type low-mercury catalyst.
Publication number is to disclose a kind of method for preparing the environment-friendly type mercury catalyst in the one Chinese patent application of CN1424142A; Spheric granules material zeolite or molecular sieve with aperture＞
, mechanical strength＞95%, Φ 4～6mm are carrier; Sodium ion through in mercury ion exchanging zeolite or the molecular sieve carrier is processed; Its mercury content reaches 3%～9%; Wherein the oxonium ion in mercury ion and the carrier forms ionic bond and firmly is fixed in the carrier, and the heat endurance of mercury is high, is 1.5 times of physical absorption; Catalytic capability makes moderate progress, and has reduced the loss of mercury.Its shortcoming is that the Hg element still is exposed to carrier surface, though strengthen to some extent with the binding ability of carrier, but still have the Hg element distillation of few part, pollute, cause catalyst that bigger toxicity is arranged, exist technological deficiency.
Publication number is the preparation method who discloses a kind of catalyst without mercury in the one Chinese patent application of CN101670293A, and this catalyst system is made up of noble metal bismuth, phosphorus catalyst and carrier, good catalyst activity, and selectivity is high, intensity is high and renewable.Its shortcoming is catalytic activity and HgCl
2Catalyst still has gap, and catalyst preparation is loaded down with trivial details, after needing to transform existing apparatus, just can come into operation, and exists that catalytic efficiency is not high, catalyst preparation process is loaded down with trivial details, has increased technological deficiency such as equipment cost.
Summary of the invention
The invention provides a kind of environment friendly chlorinated mercury metallic catalyst; Through the heterogeneous mercury chloride metallic catalyst of polymer film parcel, this catalyst has characteristics such as catalytic efficiency height, toxicity is little, catalyst release is mild in the reaction of acetylene hydrochlorination production vinyl chloride.
The present invention also provides a kind of preparation method of environment friendly chlorinated mercury metallic catalyst, in its preparation process, needs the parameter of control few, the method favorable reproducibility, and controllability is strong, is easy to suitability for industrialized production.
A kind of environment friendly chlorinated mercury metallic catalyst is formed by heterogeneous mercury chloride metallic catalyst with the polymer that the form of film is coated on heterogeneous mercury chloride metallic catalyst surface.This catalyst is divided into two-layer from outside to inside: wherein internal layer is HgCl
2Heterogeneous catalysis, skin is a polymer; Because the Hg molecular diameter is big, even distil, the diffusion in polymer film is also very slow, can effectively reduce the loss of Hg, reduces environmental pollution.
The described heterogeneous mercury chloride metallic catalyst and the weight ratio of polymer are preferably 0.01～100, further are preferably 0.1～10.
Described polymer is selected styrol copolymer (like the styrene-propene acid copolymer) for use; Ethylene copolymer; Propylene copolymer; 4 methyl 1 pentene copolymer; Polyacrylonitrile; Polyvinyl alcohol; Polyvinyl chloride; Vingon (PVDF); Polystyrene; Regenerated cellulose; Celluloid; Cellulose acetate; Ethyl cellulose; The bisphenol type polysulfones; Polyether sulphone; Phenolic polyether sulphone; Polyether-ketone; Fatty polyamide; Polysulfonamides; The aliphatic diacid polyimides; Full aromatic polyimide; Fluorinated polyimide; Polyester; Polyethylene and ethylene copolymers; Dimethyl silicone polymer; Gather the trimethyl silicane propine; Polytetrafluoroethylene (PTFE); At least a in the Kynoar.These organic polymers are prone to be dissolved in formation polymer homogeneous phase solution in nonpolar or the polar solvent.
Described catalyst is used for acetylene method when producing vinyl chloride, and the glassy state temperature of described polymer is preferably-80 ℃～180 ℃, more preferably-30 ℃～125 ℃; Fusing point is preferably 100 ℃～270 ℃.On the one hand, because the Hg molecular diameter is big, even distil, the diffusion in the polymer film of glassy state is also very slow, helps reducing the loss of Hg; On the other hand; Because the reaction temperature of acetylene method is at 170 ℃～200 ℃; Under this temperature, polymer is in viscoelastic attitude or molten state, and the sub-chain motion of polymer is violent; Under 170 ℃～200 ℃ high temperature, help the inside and outside diffusion in catalyst of reaction monomers and product, thereby under the prerequisite that guarantees production efficiency, reduce pollution environment.Because initial reaction stage exists reaction monomers in the inner resistance to mass tranfer of catalyst, it is mild to make that catalyst activity discharges, and helps control and produces.
Described heterogeneous mercury chloride metallic catalyst comprises mercuric chleride catalyst and inorganic carrier; Described mercuric chleride catalyst is carried on the inorganic carrier; Heterogeneous mercury chloride metallic catalyst of the present invention can pass through prior art for preparing, as adopting infusion process mercury chloride is carried on the inorganic carrier.Described inorganic carrier is selected the bigger inorganic carrier of rigidity for use, like activated carbon, zeolite, molecular sieve, CuO, Cu
2O, V
2O
5, Cr
2O
3, MnO
2, MoO
3, Fe
2O
3, TiO
2Deng in a kind of.
The preparation method of described environment friendly chlorinated mercury metallic catalyst may further comprise the steps:
1) polymer is dissolved in the good solvent of said polymer processes polymer solution;
2) heterogeneous mercury chloride metallic catalyst is introduced in the polymer solution in the step 1), mixes and process slurries;
3) non-solvent of said polymer is added step 2) in the slurries that make; Make polymer from solution, separate out and be deposited on the surface of heterogeneous mercury chloride metallic catalyst; Isolate deposition, deposition obtains environment friendly chlorinated mercury metallic catalyst after washing, drying.
Described good solvent is selected at least a in n-hexane, cyclohexane, benzene,toluene,xylene, carbon tetrachloride, ethyl acetate, MEK, dichloroethanes, chloroform, chlorobenzene, acetone, cyclohexanone, oxolane, carbon disulfide, pyridine, P-Dioxane, dibutyl phthalate, dimethyl formamide, methyl alcohol, ethanol, n-butanol, acetic acid, formic acid, cresols, the phenol for use; Described good solvent is that polymer provides solvent environment, can not influence activity of such catalysts.
Said non-solvent is selected from least a in ethane, butane, propane, iso-butane, pentane, isopentane, n-hexane, cyclohexane, the heptane, and non-solvent is introduced in the polymer solution, can make polymer in the solution be separated and separate out.
The present invention selects suitable good solvent and non-solvent according to selected polymer.
The liquid volume ratio of described non-solvent and described good solvent is 0.05～20.
In the step 3), the interpolation speed of described non-solvent be 0.1ml/min to 50ml/min, preferred 0.5ml/min wherein, adds the volume that speed is meant the gaseous state non-solvent of per minute adding to 10ml/min; The adding mode of described non-solvent preferably adds in the process that stirs slurries continuously, so that the polymer of separating out can be deposited on the heterogeneous catalysis surface more uniformly.
Described catalyst can be used for the reaction that the catalyzing acetylene hydrochlorinate is produced vinyl chloride.
The present invention has following advantage:
The environment friendly chlorinated mercury metallic catalyst of the present invention; Through the heterogeneous mercury chloride metallic catalyst of polymer film parcel; Can prevent the distillation of mercury element on the one hand, have the advantage that toxicity is low, pollution is little, solve traditional high problem of mercuric chleride catalyst toxicity; On the other hand; The sub-chain motion of polymer is violent, under 170 ℃～200 ℃ high temperature, helps the inside and outside diffusion in catalyst of reaction monomers and product, has guaranteed the catalytic activity that mercuric chleride catalyst is high; Also have; Initial reaction stage exists reaction monomers in the inner resistance to mass tranfer of catalyst, and it is mild to make that catalyst activity discharges, and helps control and produces.
The environment friendly chlorinated mercury metallic catalyst of the present invention has advantages such as toxicity is little, catalytic efficiency is high, catalyst release is mild in the reaction of acetylene hydrochlorination production vinyl chloride.
The preparation method of the environment friendly chlorinated mercury metallic catalyst of the present invention needs the parameter of control few, favorable reproducibility, and controllability is strong, is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the HgCl of active carbon adsorption among the embodiment 1
2The SEM figure of catalyst;
Fig. 2 is the SEM figure of environment friendly chlorinated mercury metallic catalyst among the embodiment 1.
The specific embodiment
Embodiment 1
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%, and SEM schemes like Fig. 1) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.The SEM figure of the environment friendly chlorinated mercury metallic catalyst that makes is as shown in Figure 2; Through with the contrast of Fig. 1; The surface of finding environment friendly chlorinated mercury metallic catalyst obviously is uniformly coated with a skim, and explain that environment friendly chlorinated mercury metallic catalyst is divided into two-layer from outside to inside: wherein internal layer is the HgCl of active carbon adsorption
2Catalyst, skin is a styrene-propene acid copolymer film.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 99.2%, chloro ethylene yield 99.1%.
Embodiment 2
(1) with 3g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 32.7g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 32.5g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 99.1%, chloro ethylene yield 99.2%.
Embodiment 3
(1) with 300g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 500ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 328.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 100g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.8%, chloro ethylene yield 98.9%.
Embodiment 4
(1) the bisphenol type polysulfones is dissolved fully 30g bisphenol type polysulfones (the glassy state temperature is 180 ℃, and fusing point is 170 ℃) adding 300ml dimethyl formamide (DMF) and stirring, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.8%, chloro ethylene yield 99.3%.
Embodiment 5
(1) PVDF is dissolved fully 30g Kynoar (PVDF) (the glassy state temperature is-39 ℃, and fusing point is 170 ℃) adding 300ml dimethylacetylamide (DMAc) solvent and stirring, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 99.2%, chloro ethylene yield 98.9%.
Embodiment 6
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 0.1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.6%, chloro ethylene yield 98.9%.
Embodiment 7
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 50ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.8%, chloro ethylene yield 99%.
Embodiment 8
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml cyclohexane in 80 ℃ of evaporations; Mode with the gas phase cyclohexane feeds (the adding speed of cyclohexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with cyclohexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.2%, chloro ethylene yield 98%.
Embodiment 9
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g active carbon adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml normal heptane in 108 ℃ of evaporations; Mode with the gas phase normal heptane feeds (the adding speed of normal heptane is 50ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with normal heptane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.2%, chloro ethylene yield 98.4%.
Embodiment 10
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) add 30g Al
2O
3The HgCl of absorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 50ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 97.9%, chloro ethylene yield 97.6%.
Embodiment 11
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) HgCl of adding 30g molecular sieve adsorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 4000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 50ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 58.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 55.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.9%, chloro ethylene yield 98.2%.
Embodiment 12
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) add 30g Al
2O
3The HgCl of absorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 15ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 52.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 50.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.4%, chloro ethylene yield 98.6%.
Embodiment 13
(1) with 30g styrene-propene acid copolymer (weight average molecular weight Mw=11300; Molecular weight distribution MWD=1.31; The glassy state temperature is 125 ℃, and fusing point is 215 ℃) add 300ml oxolane (THF) and stir the styrene-propene acid copolymer is dissolved fully, make polymer solution;
(2) add 30g Al
2O
3The HgCl of absorption
2Catalyst (wherein the Hg weight percentage is 13.1%) mixes the catalyst that forms the slurries shape to polymer solution;
(3) with the 6000ml n-hexane in 66 ℃ of evaporations; Mode with the gas phase n-hexane feeds (the adding speed of n-hexane is 1ml/min) fully and keeps in the catalyst of slurries shape of step (2) preparation of stirring; Stop then stirring, the precipitated solid thing, extract suspension liquid out, with n-hexane washing precipitation solids 3 times; Promptly make environment friendly chlorinated mercury metallic catalyst, amount to 59.5g.
(4), be used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution with the environment friendly chlorinated mercury metallic catalyst 59.0g that makes in the step 3)
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 98.9%, chloro ethylene yield 99.2%.
Comparative Examples 1
Get the HgCl of active carbon adsorption among the embodiment 1
2Catalyst 30.0g is used for the reaction that acetylene hydrochlorination is produced vinyl chloride, the mol ratio C of reaction distribution
2H
2/ HCl=1/1.5, air speed 11ml/h reacts under 170 ℃ condition, and the hydrogen chloride soak time is 2h.Analytical reactions tail gas, the conversion ratio of acetylene is 99%, vinyl chloride selectivity 99%.Through intelligent gravimetric balance (IGA), measure the HgCl of the active carbon adsorption in the Comparative Examples 1
2Environment friendly chlorinated mercury metallic catalyst in time weight change situation at room temperature among catalyst and the embodiment 1.Use high purity nitrogen to be carrier gas; The weight change of 200mg catalyst in 10 days observed in experiment, and catalyst (the environment friendly chlorinated mercury metallic catalyst) weight that discovery is coated with polymer is stable, and any weightlessness does not take place; Show that at room temperature the Hg metallic catalyst distillation does not take place and runs off.And the catalyst of the coated polymer film (HgCl of active carbon adsorption not
2Catalyst), in 10 days, accumulate weightless 0.25wt%.
Claims (5)
1. an environment friendly chlorinated mercury metallic catalyst is characterized in that, forms by heterogeneous mercury chloride metallic catalyst with the polymer that the form of film is coated on heterogeneous mercury chloride metallic catalyst surface;
Described polymer is a styrol copolymer; Ethylene copolymer; Propylene copolymer; 4 methyl 1 pentene copolymer; Polyacrylonitrile; Polyvinyl alcohol; Polyvinyl chloride; Vingon; Polystyrene; Regenerated cellulose; Celluloid; Cellulose acetate; Ethyl cellulose; The bisphenol type polysulfones; Polyether sulphone; Phenolic polyether sulphone; Polyether-ketone; Fatty polyamide; Polysulfonamides; The aliphatic diacid polyimides; Full aromatic polyimide; Fluorinated polyimide; Polyester; Dimethyl silicone polymer; Gather the trimethyl silicane propine; Polytetrafluoroethylene (PTFE); In the Kynoar one or more;
The described heterogeneous mercury chloride metallic catalyst and the weight ratio of polymer are 0.1～10;
Described heterogeneous mercury chloride metallic catalyst is the mercuric chleride catalyst that is carried on the inorganic carrier;
Described inorganic carrier is activated carbon, zeolite, molecular sieve, CuO, Cu
2O, V
2O
5, Cr
2O
3, MnO
2, MoO
3, Fe
2O
3Or TiO
2
2. the preparation method of environment friendly chlorinated mercury metallic catalyst according to claim 1 is characterized in that, may further comprise the steps:
1) polymer is dissolved in the good solvent of said polymer processes polymer solution;
2) heterogeneous mercury chloride metallic catalyst is introduced in the polymer solution in the step 1), mixes and process slurries;
3) non-solvent of said polymer is added step 2) in the slurries that make, make polymer from solution, separate out and be deposited on the surface of heterogeneous mercury chloride metallic catalyst, obtain environment friendly chlorinated mercury metallic catalyst.
3. the preparation method of environment friendly chlorinated mercury metallic catalyst according to claim 2; It is characterized in that described good solvent is one or more in benzene,toluene,xylene, carbon tetrachloride, ethyl acetate, MEK, dichloroethanes, chloroform, chlorobenzene, acetone, cyclohexanone, oxolane, carbon disulfide, pyridine, P-Dioxane, dibutyl phthalate, dimethyl formamide, methyl alcohol, ethanol, n-butanol, acetic acid, formic acid, cresols, the phenol;
Described non-solvent is one or more in ethane, butane, propane, pentane, n-hexane, cyclohexane, the heptane.
4. according to the preparation method of claim 2 or 3 described environment friendly chlorinated mercury metallic catalysts, it is characterized in that the liquid volume ratio of described non-solvent and described good solvent is 0.05～20.
5. the preparation method of environment friendly chlorinated mercury metallic catalyst according to claim 2 is characterized in that, in the step 3), the interpolation speed of described non-solvent is counted 0.1ml/min to 50ml/min with the volume of gaseous state non-solvent.
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| CN103170371A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN103170372A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene through acetylene gas phase hydrochlorination |
| CN103203241B (en) * | 2013-04-25 | 2014-12-17 | 新疆天业（集团）有限公司 | Low-mercury catalyst for hydrochlorination of acetylene |
| CN105195230B (en) * | 2015-10-27 | 2017-12-26 | 宁夏新龙蓝天科技股份有限公司 | A kind of method that low-mercury catalyst is prepared using high iodine number activated carbon |
| CN105582967B (en) * | 2015-12-25 | 2018-10-09 | 贵州泰柏妇科疾病研究中心 | A kind of nanoscale low mercury catalyst |
| CN106622038B (en) * | 2016-12-08 | 2023-06-27 | 北京化工大学 | Supported insert of superfine fiber membrane electrostatic adsorption catalyst and application method thereof |
| CN108097307B (en) * | 2018-01-10 | 2020-08-21 | 南开大学 | Preparation method and use method of metal-free catalyst for preparing vinyl chloride from fixed bed acetylene |
| CN110227507B (en) * | 2019-06-17 | 2021-12-07 | 浙江工业大学 | High-stability ultralow-mercury catalyst and preparation method and application thereof |
| CN112844433B (en) * | 2021-01-14 | 2023-04-14 | 石河子大学 | Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof |
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