CN102049260B - Microsphere ethylene oxychlorination catalyst and preparation method thereof - Google Patents
Microsphere ethylene oxychlorination catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a microsphere ethylene oxychlorination catalyst and a preparation method thereof. The catalyst comprises one of Cu, Mg, and K, rare-earth elements and a gamma-alumina carrier. The preparation method of the catalyst comprises the steps of solution preparation, precipitation reaction, peptization, homogenization of active components and auxiliary components, atomization formation, and subsequent treatment. With the method, a solution of active components and a solution of auxiliaries are dissolved in slurry subjected to peptization, and a certain amount of pore-expanding agent is added in a sol solution subjected to slurry beating, therefore the uniform distribution of active components and auxiliary components in the sol solution is ensured, and meanwhile the added pore-expanding agent can expand the pore paths of a molded microsphere structure during atomization, the pore path volume of the catalyst carrier is increased and the pore volume and the specific surface area of the catalyst are increased.
Description
Technical field
The present invention relates to a kind of ethylene oxychlorination catalyst and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is one of five large resins for universal use, has the outstanding features such as abundant raw material, manufacturing process be ripe, cheap, of many uses, has now become the second largest resins for universal use that is only second in the world polyvinyl resin.Polyvinyl chloride is easily processed, can be processed by modes such as mold pressing, laminated, injection moulding, extrusion molding, calendering, blowing hollows, therefore be widely used in plastics soft goods such as producing artificial leather, film, trunking, and produce the plastics boardy product fields such as sheet material, door and window, pipeline and valve.
Polyvinyl chloride is formed by vinyl chloride (VCM) monomer polymerization, vinyl chloride is the important Organic Chemicals of a kind of large-tonnage, its overwhelming majority is for the production of polyvinyl chloride resin, and the vinyl chloride expense account for 60～70% of polyvinyl chloride production cost, so thereby improve the vinyl chloride production technology and reduce its production cost and will directly have influence on the production cost of polyvinyl chloride.
In prior art, the production technology for preparing vinyl chloride of domestic normal employing has carbide acetylene method and oil ethylene process.Wherein, there is the problems such as energy consumption is large, catalyst mercury pollution due to carbide acetylene method, thereby make the oil ethylene process become vinyl chloride preparation method the most commonly used.The oil ethylene process is to take ethene as raw material, through ethylene oxychlorination, prepares dichloroethanes (EDC), then carries out cracking by dichloroethanes and obtain vinyl chloride.In above-mentioned preparation method, ethylene oxychlorination need to carry out under the oxychlorination catalyst effect, and the catalytic performance of catalyst will directly affect the production efficiency that ethylene oxychlorination prepares vinyl chloride so, and then affects its production cost.
In prior art, ethylene oxychlorination catalyst commonly used be take copper as main active component, these help active component also further to have added rare earth metal, alkali metal or alkaline-earth metal, and above-mentioned active component is deposited on and forms on alundum (Al2O3), silica, diatomite, clay, bleaching earth or vanadine particulate vector.
The catalytic performance of catalyst and the preparation method of catalyst have direct relation.At present, what the preparation method of ethylene oxychlorination catalyst of the prior art generally adopted is the method for infusion process and coprecipitation combination, such as Chinese patent CN100457260C and CN1164363C.Wherein, the disclosed oxychlorination catalyst of Chinese patent CN1164363C is by the aluminum oxide micro-sphere of cupric 8～13wt%, at least one rare earth metal in lanthanum, cerium, praseodymium, yttrium that is selected from that content is 1.0～5.0wt%, and at least one alkali metal that content is 1.0～2.5wt% forms.In prior art, for the understanding of ethylene oxychlorination catalyst, the known ethylene oxychlorination of those of ordinary skills is followed the Deacon course of reaction, and it is at high temperature with copper salt, to make catalyst, realizes oxi-chlorination.As main active component, in order to obtain better catalyst activity, generally all can select larger copper content, to guarantee obtaining the as far as possible ethylene oxychlorination catalyst had than large pore volume and specific area, but the restriction just because of above-mentioned theory, make the ethylene oxychlorination catalyst in the prior art of the content proportioning with said components show after tested, its pore volume only has 0.3～0.4ml/g, and specific area can only reach 130～220m
2/ g.
Also further disclose in the prior art the preparation method of this oxychlorination catalyst, it mainly is divided into two-part step: the first, adopt coprecipitation to prepare the alumina support microballoon; Ratio according to the required composition of catalyst, the hydrochloric acid solution and the sodium aluminate solution that prepare respectively cupric oxide, above-mentioned two kinds of solution are mixed according to a certain percentage, in 20～60 ℃, pH value equal under 7.0～9.0 condition and plastic, obtain coprecipitate and filter; Above-mentioned coprecipitate water is carried out to pulp, spray drying forming; Utilize afterwards alkaline solution to be washed article shaped, through follow-up filtration and dry the processing, obtain the copper-containing alumina microballoon.The second, adopt infusion process will help active constituent loading on carrier microballoons; With the salting liquid of alkali metal and rare earth metal, the copper-containing alumina microballoon prepared in above-mentioned first step is flooded, make alkali metal and rare earth metal be carried on containing on the aluminum oxide micro-sphere of main active ingredient copper, and above-mentioned aluminum oxide micro-sphere after dipping is carried out to follow-up drying and calcination process.
At first above-mentioned preparation method adopts coprecipitation to realize the load of main active ingredient copper on carrier when preparing carrier granular, re-uses afterwards infusion process and realizes helping the further load of active component on the aluminum oxide micro-sphere carrier; The method adopts and first precipitates the method for flooding afterwards, to precipitate and dipping is divided into two steps and carries out, help like this distribution of active component on carrier to be limited to the effect of dipping, in general, adopt infusion process easily to cause the dispersion of active component on carrier inhomogeneous, thereby affect the catalytic activity of catalyst.
In addition, in above-mentioned preparation method, it is when adopting coprecipitation to prepare the copper-containing alumina carrier microballoons, use coprecipitation to prepare alumina support in conjunction with the spray drying forming technology, the pore structure denser of the microspherical catalyst that it prepares, duct is narrower, active component is not easy fully to enter inside, microballoon duct, thereby make the effective ratio area of catalyst reduce, in addition, active component can't fully enter inside, microballoon duct and also make the active component after dipping very easily at high temperature distil in follow-up use procedure and lose, thereby catalytic activity and the catalytic selectivity of catalyst have been affected.
Summary of the invention
First technical problem to be solved by this invention is that ethylene oxychlorination catalyst of the prior art all improves pore volume and the specific area of catalyst always by improving as far as possible copper content in catalyst, but owing to just improving as far as possible copper content, do not have the Optimum Contents between each component in the hormany catalyt agent, so cause pore volume and the specific area of the ethylene oxychlorination catalyst for preparing to be confined in certain number range of the prior art always, thereby and then provide a kind of by regulating copper and the proportioning higher pore volume of acquisition of other active components and adjuvant component and the ethylene oxychlorination catalyst of specific area in catalyst.
Second technical problem to be solved by this invention is the aluminum oxide micro-sphere carrier that in prior art, at first ethylene oxychlorination catalyst adopts the coprecipitation preparation to contain main active component, adopt again afterwards infusion process to realize that other help the load of active component on the aluminum oxide micro-sphere carrier, this preparation method adopts follow-up independently infusion process easily to cause the dispersion of active component on carrier inhomogeneous, thereby affect the problem of the catalytic activity of catalyst, and then provide a kind of and can in the process for preparing the aluminum oxide micro-sphere carrier, realize main active component simultaneously and help the uniform load of active component, utilize coprecipitation and infusion process coupling to prepare the method for ethylene oxychlorination catalyst.
The 3rd technical problem to be solved by this invention is in available technology adopting coprecipitation and the process of infusion process in conjunction with the preparation ethylene oxychlorination catalyst, the alumina support that uses coprecipitation to prepare in conjunction with the spray drying forming technology, the pore structure denser of its microballoon, duct is narrower, active component is not easy fully to enter inside, microballoon duct, thereby make the effective ratio area of catalyst reduce, also make the active component after dipping very easily at high temperature distil in follow-up use procedure and lose, thereby the catalytic activity of catalyst and the problem of catalytic selectivity have been affected, and then provide a kind of microballoon pore structure that can alumina support to expand, and the preparation method of the ethylene oxychlorination catalyst of raising catalyst effective ratio area and catalyst activity and selectivity.
For solving the problems of the technologies described above, the invention provides a kind of ethylene oxychlorination catalyst, it is comprised of following component: at least one the 0.2～2wt% in copper 4～7.5wt%, magnesium and potassium, rare earth element 0.1～1.0wt%, gamma-aluminium oxide carrier 81.0～91.0wt%, surplus is chlorion and impurity.
The present invention also, on the basis that discloses above-mentioned ethylene oxychlorination catalyst, further discloses the preparation method of this ethylene oxychlorination catalyst, and it comprises the steps:
(a) aluminium hydrate powder is joined in sodium hydroxide solution, set temperature is 95～125 ℃ and is reacted, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 1.15～2.25%;
The acid solution that the preparation mass percentage concentration is 25～40%;
Preparation active component solution and compounding agent solution;
(b) described sodium aluminate solution and described acid solution are mixed under stirring, reaction temperature is set is 30～70 ℃, pH value and be 5～9 is reacted, be precipitated after filtering thing, utilize deionized water to be washed to eluent described sediment and stop for neutrality, obtain wet cake;
(c) described wet cake is added in the peptization still, and add the deionized water that is equal to or greater than described wet cake weight, then add the peptizing agent of described wet cake weight 0.5～2.5%, the peptization of pulling an oar under the high-speed stirred that is 300 ~ 500r/min at rotating speed;
(d) active component solution and compounding agent solution are joined in the sol solution that step (c) makes, add respectively wherein organic expanding agent, the amount of described organic expanding agent is 0.1～0.5% of described wet cake weight, obtains the mixed liquid of peptization simultaneously;
(e) the mixed liquid of the above-mentioned peptization after peptization is sent in the spray shaping drying tower and carried out spray shaping, it is 450～600 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 100～160 ℃, the time of staying 3～10s in described spray shaping drying tower, obtain microspherical catalyst parent after drying;
(f) the microspherical catalyst parent made in step (e) being carried out to roasting under 300～800 ℃ gets final product.
Wherein, the described reaction temperature in described step (b) is preferably 40～50 ℃, and the reaction time is 1～2h.Described pH value in described step (b) is preferably 6.5～8.
The amount of the described deionized water added in described step (c) is 1～1.5 times of described wet cake weight.The amount of the described peptizing agent added is 1.0～1.5% of described wet cake weight.Described peptizing agent is salpeter solution or the citric acid solution that mass percentage concentration is 30～50%.Making beating peptization 1～2h under the high-speed stirred that is 300～500r/min at rotating speed in described step (c).
Described organic expanding agent is carboxymethyl cellulose, starch derivatives.
In described step (f) by the microspherical catalyst parent in 450～650 ℃ of lower roasting 2～4h.
Wherein, described starch derivatives comprises dextrin, sugar alcohol, converted starch and starch hydrolysate etc.
The preparation method of microspherical ethylene oxychlorination catalyst of the present invention, mainly be divided into six steps, is respectively solution preparation, precipitation reaction, peptization processing, active component and adjuvant component homogenizing, spray shaping, subsequent treatment.Below will be described in detail above steps:
The first, solution preparation, be used for preparing sodium aluminate solution, acid solution and active component solution and compounding agent solution;
Wherein, when the preparation sodium aluminate solution, aluminium hydrate powder is joined in sodium hydroxide solution, by the reaction generation sodium metaaluminate product of the two; It is 95～125 ℃ that reaction temperature is set in this reaction, and this temperature setting is equipped with and is beneficial to fully carrying out of reaction.
The sodium aluminate solution that preparation alundum (Al2O3) and NaOH percentage by weight are 1.15～2.25% is because only meeting on the basis of above-mentioned condition, just can guarantee finally to prepare ethylene oxychlorination catalyst and have suitable pore volume and suitable specific area; Wherein, suitable pore volume and specific area refer to that the pore volume of catalyst and specific area can not be too little, the specific area of the too little correspondingly catalyst of pore volume also can be little, the too little activity that affects catalyst of the effective active area of catalyst like this, the specific area of the too large so correspondingly catalyst of pore volume is just large, will have influence on the mechanical strength of catalyst, easily cause breaking of catalyst, produce powder phenomenon-tion.
Selecting the acid solution that the preparation mass percentage concentration is 25～40%, is to consider its impact on follow-up spray-drying step, selects to arrange the slurries thickness that acid solution that concentration is larger easily causes follow-up solation to obtain, and is unfavorable for that spraying processes; Concentration is too rare can be made needs the volume of the acid solution that adds to increase in the precipitation reaction step, finally can increase the processing time of filtering precipitate after precipitation reaction, also will inevitably make the corresponding increase of water content in wet cake simultaneously, and then have influence on again in the spray-drying step, make the amount of slurry of solation increase, extended the required time of spray shaping.
The second, precipitation reaction, described sodium aluminate solution and described acid solution are mixed under stirring, reaction temperature is set is 30～70 ℃, pH value and be 5～9 is reacted, be precipitated after filtering thing, utilizing deionized water to be washed to eluent described sediment stops for neutrality, obtains wet cake;
At first described sodium metaaluminate and acid solution are mixed under stirring, thereby in carrying out, with plastic, reaction generates aluminum hydroxide precipitation; Wherein, for the mixing of sodium metaaluminate and acid solution, can use one-dimensional method also can use cocurrent process, wherein, use one-dimensional method in sodium aluminate solution, to add gradually the acid solution mixing, described cocurrent process is that sodium metaaluminate and acid solution are distinguished continuous charging simultaneously.In the selection of above-mentioned one-dimensional method and cocurrent process, preferred cocurrent process.Show after testing, use the difference of cocurrent process due to feed way, make the catalyst pore volume prepared larger than the catalyst pore volume that uses one-dimensional method to obtain.
Described reaction temperature is set in above-mentioned reaction being 30～70 ℃ is 5～9 with the pH value, it is 6.5～8 with the pH value that temperature is preferably 40～50 ℃, be because the reaction of only carrying out sodium metaaluminate and acid solution under this temperature and pH value condition can guarantee that the crystalline phase of the catalyst carrier alundum (Al2O3) that finally prepares is the γ type as far as possible, and guarantee that the catalyst prepared has suitable pore volume.
In this step, also need to utilize deionized water to be washed the sediment obtained, why to wash to described eluent to neutral, be because eluent when neutral, illustrate that sediment also has been neutrality, without acidic materials, avoided in down-stream the corrosion to equipment.
Three, peptization is processed, described wet cake is added in the peptization still, and add the deionized water that is equal to or greater than described wet cake weight, then add the peptizing agent of described wet cake weight 0.5～2.5%, the peptization of pulling an oar under the high-speed stirred of rotating speed 300～500r/min;
Add deionized water in described wet cake, the weight of described deionized water will be equal to or greater than the weight of wet cake, is preferably 1～1.5 times of weight, and purpose is in order to obtain as far as possible little slurry concentration, to be convenient to like this spray shaping; Afterwards, add peptizing agent in described wet cake, and the amount of selecting described peptizing agent is 0.5～2.5% of wet cake weight, be preferably 1.0～1.5%, the amount of peptizing agent is too little can't be realized sedimentary abundant solation, although realized that too greatly sedimentary abundant solation still but easily causes dissolved adhesiveness to increase, and is unfavorable for the slurry spray shaping.
In above-mentioned preparation process, also need the solution after peptization is carried out to the stirring to pulp processing, the rotating speed that high-speed stirred is set is that 300～500r/min is the effective rotating speed that is beneficial to the homogenize of colloidal sol slurry that can realize.
Four, active component and adjuvant component homogenizing, join active component solution and compounding agent solution in the sol solution that step (c) makes, and adding wherein organic expanding agent, the amount of described organic expanding agent is 0.1～0.5% of described wet cake weight simultaneously;
Add active component solution and compounding agent solution in this step, realize the abundant mixing of above-mentioned solution and solation disposed slurry, this step is to be different from the committed step of prior art in the present invention, all main active components and the abundant mixing that helps active component and catalyst carrier predecessor have been realized in this step, have laid a good foundation so just to follow-up catalyst spray shaping, realized the dispersed of all active materials and carrier mass, in the catalyst that is conducive to obtain after spray shaping, the active component uniform load is on the catalyst carrier of while moulding.
Thereby add the specific area that a certain amount of organic expanding agent can improve the pore volume raising catalyst in the catalyst microspheres carrier duct prepared in sol solution.Above-mentioned expanding agent is selected organic substance, to consider that organic substance is when realizing its above-mentioned functions, can be in subsequent processes, realize removing it by hot environment, select inorganic matter can't realize above-mentioned purpose, so just easily due to the existence of other ions, affect the catalytic performance of catalyst.
The amount of described organic expanding agent must be appropriate, measure too littlely can't realize above-mentioned purpose, the too large spray shaping that is unfavorable for slurry of amount.
Five, spray shaping, the mixed liquid of peptization after peptization is sent in the spray shaping drying tower and carried out spray shaping, it is 450～600 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 100～160 ℃, the time of staying 3～10s in described spray shaping drying tower, obtain microspherical catalyst parent after drying;
Sol solution is through spray shaping, in this process, just utilize hot blast to be processed the catalyst Precursors in forming process, the hot blast inlet temperature must be set to 450～600 ℃, can in the process of catalyst Precursors moulding, to it, carry out constantly dry and the moisture in its moulding slurry is thoroughly volatilized as much as possible like this, after the continuous exchange heat circulation through said process, the hot-blast outlet temperature will reach 100～160 ℃.Time for above-mentioned spray shaping drying is necessary for 3～10s, the time of staying is on the basis that guarantees fully to complete to the drying of catalyst Precursors, can not be oversize, easily under hot environment, break away from moisture balance, make catalyst Precursors after drying again realize with dry environment under steam the absorption exchange occurs.
Six, subsequent treatment is carried out roasting to above-mentioned microspherical catalyst parent and is got final product under 300～800 ℃.In this processing procedure, preferred described sintering temperature is 450～650 ℃, and roasting time is 2～4h.In this step, limit sintering temperature can not be too high can not be too low, the too low meeting of temperature reduces the wearability of catalyst, excess Temperature can destroy the phase structure of catalyst, affects catalyst performance; Only in this temperature range, the catalyst Precursors prepared is carried out to calcination process, just can obtain required for the present invention want take the ethylene oxychlorination catalyst that γ-alundum (Al2O3) is carrier.
The above-mentioned preparation method of ethylene oxychlorination catalyst of the present invention, reaction by aluminium hydroxide solution and sodium hydroxide solution generates sodium aluminate solution, and further utilize the reaction of sodium aluminate solution and acid solution again to prepare alumine hydroxide colloid, above-mentioned two preparation process have realized the purifying to alumine hydroxide colloid, the stability of the catalyst performance that has guaranteed to utilize this colloid to prepare.And after above-mentioned colloid is carried out to the peptization making beating, directly do not carry out routine operation spray drying forming catalyst carrier of the prior art, but will prepare the required active component solution of ethylene oxychlorination catalyst and compounding agent solution is added in sol solution, realize the abundant mixing of active component and adjuvant component and support precursor, just realized so main active component and adjuvant component being uniformly distributed on alumina support after utilizing spray shaping.
The present invention has advantages of as described below:
(1) ethylene oxychlorination catalyst of the present invention is comprised of following component: at least one the 0.2～2wt% in copper 4～7.5wt%, magnesium and potassium, rare earth element 0.1～1.0wt% and gamma-aluminium oxide carrier.Find after deliberation, suitably reduce copper content, and regulate the Optimum Contents of other auxiliary component magnesium, potassium and rare earth element to there is higher pore volume and the specific area of ethylene oxychlorination catalyst of higher copper content in can obtaining compared to prior art; Data show that pore volume improves approximately 20%, specific area improves approximately 5%, the raising of above-mentioned data, for large-scale dichloroethanes production, because output is very large, can obtain high as far as possible dichloroethanes conversion ratio so increase a little the above-mentioned performance of ethylene oxychlorination catalyst, there is high economic worth.
(2) preparation method of microspherical ethylene oxychlorination catalyst of the present invention, after the alumine hydroxide colloid to after purified is pulled an oar solation, active component solution and compounding agent solution are dissolved in the slurry after solation, realized dispersed in the precursor solution of ethylene oxychlorination catalyst carrier of active component and auxiliary agent, thereby guaranteed to prepare the catalyst activity component can uniform load on catalyst carrier, thereby guaranteed the catalytic activity of ethylene oxychlorination catalyst, the active material of having avoided the available technology adopting infusion process easily to cause skewness and then affect the problem of catalyst catalytic performance on carrier, in addition, also in the sol solution after making beating, add appropriate expanding agent in the preparation method of ethylene oxychlorination catalyst of the present invention, can be in the process that sol solution is sprayed the expansion effect be played in the duct of the micro-sphere structure of moulding, thereby improved the duct volume of catalyst carrier, and then improved pore volume and the specific area of catalyst.
(3) preparation method of microspherical ethylene oxychlorination catalyst of the present invention, reaction by aluminium hydroxide solution and sodium hydroxide solution generates sodium aluminate solution, and further utilize the reaction of sodium aluminate solution and acid solution again to prepare alumine hydroxide colloid, realized the purifying to the aluminium hydroxide material, guaranteed not to be subject to the impact of other its catalytic performances of ion pair in the process of preparation ethylene oxychlorination catalyst.
(4) use catalyst that the preparation method of microspherical ethylene oxychlorination catalyst of the present invention prepares to have the physical property of following excellence: bulk density is 0.8～1.2g/ml, and specific area is 150～230m
2/ g, pore volume is 0.43～0.6ml/g, particle mean size is 40～70 μ m.
The specific embodiment
embodiment 1
Take the 1000g aluminium hydrate powder, it is joined in the sodium hydroxide solution that the 1200ml mass percentage concentration is 30%, set temperature is 95 ℃ and is reacted, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 1.15%;
The hydrochloric acid solution that the preparation mass percentage concentration is 25%;
The copper chloride active component solution that the preparation mass percentage concentration is 20%;
The magnesium chloride compounding agent solution that the preparation mass percentage concentration is 30%;
The lutecium chloride compounding agent solution that the preparation mass percentage concentration is 30%.
Use one-dimensional method the described sodium aluminate solution of 800ml to be placed in to the stillpot of self-control belt stirrer, the hydrochloric acid solution 960ml that to add gradually wherein mass percentage concentration be 25%, and turn on agitator stirred 5h to it and carry out precipitation reaction, reaction temperature is set in this reaction is 30 ℃, pH value is 9; Reaction finishes to be precipitated thing by filtration, utilizes deionized water to be washed to eluent to this sediment and stops for neutrality, obtains wet cake 640g.
Wet cake is added in the peptization still of making belt stirrer by oneself, and add wherein the deionized water 640ml that equals wet cake weight, the salpeter solution 9ml that the peptizing agent-mass percentage concentration that adds again wet cake weight 0.5% is 30%, under the high-speed stirred that is 300r/min at rotating speed, making beating peptization 1h, obtain sol solution 1050ml.
The lutecium chloride compounding agent solution 7.5ml that the magnesium chloride compounding agent solution 5ml that the copper chloride active component solution 40ml that is 20% by the quality percentage composition and mass percentage concentration are 30% and mass percentage concentration are 30% joins in above-mentioned sol solution, add wherein organic expanding agent carboxymethyl cellulose 0.64g (wet cake weight 0.1%) simultaneously, obtain the mixed liquid of peptization.
The mixed liquid 800ml of above-mentioned peptization is sent in the spray shaping drying tower and carries out spray shaping, it is 450 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 100 ℃, guarantee the time of staying 10s of article shaped in described spray shaping drying tower, obtain microspherical catalyst parent after drying; Above-mentioned microspherical catalyst parent is carried out to roasting 10h under 300 ℃ and can obtain ethylene oxychlorination catalyst A.
In this catalyst, copper content is 4%, and content of magnesium is 0.8%, and lutetium content is 1.0%, and alumina carrier content is 85.8%, and all the other are chlorion and impurity.
embodiment 2
Take the 1000g aluminium hydrate powder, it is joined in the sodium hydroxide solution that the 800ml mass percentage concentration is 30%, set temperature is 125 ℃ and is reacted, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 2.25%;
The hydrochloric acid solution that the preparation mass percentage concentration is 40%;
The copper chloride active component solution that the preparation mass percentage concentration is 20%;
The magnesium chloride compounding agent solution that the preparation mass percentage concentration is 30%;
The potassium chloride compounding agent solution that the preparation mass percentage concentration is 30%;
The lanthanum chloride compounding agent solution that the preparation mass percentage concentration is 30%.
Use one-dimensional method the described sodium aluminate solution of 800ml to be placed in to the stillpot of self-control belt stirrer, the hydrochloric acid solution 780ml that to add gradually wherein mass percentage concentration be 40%, and turn on agitator stirred 0.5h to it and carry out precipitation reaction, reaction temperature is set in this reaction is 70 ℃, pH value is 5; Reaction finishes to be precipitated thing by filtration, utilizes deionized water to be washed to eluent to this sediment and stops for neutrality, obtains wet cake 680g.
Wet cake is added in the peptization still of making belt stirrer by oneself, and add wherein the deionized water 2040ml of 3 times of wet cake weight, the salpeter solution 34ml that the peptizing agent-mass percentage concentration that adds again wet cake weight 2.5% is 50%, under the high-speed stirred that is 500r/min at rotating speed, making beating peptization 1.5h, obtain sol solution 2460ml.
The lanthanum chloride compounding agent solution 4ml that the potassium chloride compounding agent solution 2ml that the copper chloride active component solution 48ml that is 20% by the quality percentage composition, magnesium chloride compounding agent solution 4ml that mass percentage concentration is 30% and mass percentage concentration are 30% and mass percentage concentration are 30% joins in above-mentioned sol solution, add wherein organic expanding agent carboxymethyl cellulose 3.4g (wet cake weight 0.5%) simultaneously, obtain the mixed liquid of peptization.
The mixed liquid 1500ml of above-mentioned peptization is sent in the spray shaping drying tower and carries out spray shaping, it is 600 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 160 ℃, guarantee the time of staying 3s of article shaped in described spray shaping drying tower, obtain microspherical catalyst parent after drying; Above-mentioned microspherical catalyst parent is carried out to roasting 1h under 800 ℃ and can obtain ethylene oxychlorination catalyst B.
In this catalyst, copper content is 5.8%, and content of magnesium is 0.68%, and potassium content is 0.1%, and lanthanum content is 0.3%, and alumina carrier content is 83.2%, and all the other are chlorion and impurity.
embodiment 3
Take the 1000g aluminium hydrate powder, it is joined in the sodium hydroxide solution that the 1100ml mass percentage concentration is 30%, set temperature is 105 ℃ and is reacted 2h, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 1.8%;
The salpeter solution that the preparation mass percentage concentration is 40%;
The copper chloride active component solution that the preparation mass percentage concentration is 20%;
The magnesium chloride compounding agent solution that the preparation mass percentage concentration is 30%;
The cerous nitrate compounding agent solution that the preparation mass percentage concentration is 30%.
Use the salpeter solution that cocurrent process is 40% by the described sodium aluminate solution of 1000ml and 940ml mass percentage concentration to be added into gradually in the stillpot of self-control belt stirrer simultaneously, and turn on agitator stirred 1.0h to it and carry out precipitation reaction, reaction temperature is set in this reaction is 50 ℃, pH value is 7; Reaction finishes to be precipitated thing by filtration, utilizes deionized water to be washed to eluent to this sediment and stops for neutrality, obtains wet cake 820g.
Wet cake is added in the peptization still of making belt stirrer by oneself, and add wherein the deionized water 984ml of 1.2 times of wet cake weight, the salpeter solution 17ml that the peptizing agent-mass percentage concentration that adds again wet cake weight 0.8% is 35%, under the high-speed stirred that is 450r/min at rotating speed, making beating peptization 1h, obtain sol solution 1560ml.
The cerous nitrate compounding agent solution 2ml that the copper chloride active component solution 75ml that is 20% by the quality percentage composition, magnesium chloride compounding agent solution 1ml that mass percentage concentration is 30% and mass percentage concentration are 30% joins in above-mentioned sol solution, add wherein organic expanding agent carboxymethyl cellulose 0.82g (wet cake weight 0.1%) simultaneously, obtain the mixed liquid of peptization.
The mixed liquid 1000ml of above-mentioned peptization is sent in the spray shaping drying tower and carries out spray shaping, it is 500 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 150 ℃, guarantee the time of staying 8s of article shaped in described spray shaping drying tower, obtain microspherical catalyst parent after drying; Above-mentioned microspherical catalyst parent is carried out to roasting 3h under 550 ℃ and can obtain ethylene oxychlorination catalyst C.
In this catalyst, copper content is 6.7%, and content of magnesium is 0.2%, and cerium content is 0.20%, and alumina carrier content is 81.6%, and all the other are chlorion and impurity.
embodiment 4
Take the 1000g aluminium hydrate powder, it is joined in the sodium hydroxide solution that the 1100ml mass percentage concentration is 30%, set temperature is 105 ℃ and is reacted 2h, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 1.8%;
The salpeter solution that the preparation mass percentage concentration is 30%;
The copper chloride active component solution that the preparation mass percentage concentration is 20%;
The magnesium chloride compounding agent solution that the preparation mass percentage concentration is 30%;
The lanthanum chloride compounding agent solution that the preparation mass percentage concentration is 30%.
Use one-dimensional method the described sodium aluminate solution of 1000ml to be placed in to the stillpot of self-control belt stirrer, the salpeter solution 1040ml that to add gradually wherein mass percentage concentration be 30%, and turn on agitator stirred 2.0h to it and carry out precipitation reaction, reaction temperature is set in this reaction is 40 ℃, pH value is 8; Reaction finishes to be precipitated thing by filtration, utilizes deionized water to be washed to eluent to this sediment and stops for neutrality, obtains wet cake 840g.
Wet cake is added in the peptization still of making belt stirrer by oneself, and add wherein the deionized water 1260ml of 1.5 times of wet cake weight, the citric acid solution 19.8ml that the peptizing agent-mass percentage concentration that adds again wet cake weight 1.0% is 35%, under the high-speed stirred that is 450r/min at rotating speed, making beating peptization 1h, obtain sol solution 1640ml.
The lanthanum chloride compounding agent solution 3ml that the copper chloride active component solution 83ml that is 20% by the quality percentage composition, magnesium chloride compounding agent solution 6ml that mass percentage concentration is 30% and mass percentage concentration are 30% joins in above-mentioned sol solution, add wherein organic expanding agent carboxymethyl cellulose 0.84g (wet cake weight 0.1%) simultaneously, obtain the mixed liquid of peptization.
The mixed liquid 1000ml of above-mentioned peptization is sent in the spray shaping drying tower and carries out spray shaping, it is 500 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 150 ℃, guarantee the time of staying 6s of article shaped in described spray shaping drying tower, obtain microspherical catalyst parent after drying; Above-mentioned microspherical catalyst parent is carried out to roasting 2h under 650 ℃ and can obtain ethylene oxychlorination catalyst D.
In this catalyst, copper content is 7.5%, and content of magnesium is 1.08%, and lanthanum content is 0.29%, and alumina carrier content is 81.0%, and all the other are chlorion and impurity.
embodiment 5
Take the 1000g aluminium hydrate powder, it is joined in the sodium hydroxide solution that the 1100ml mass percentage concentration is 30%, set temperature is 105 ℃ and is reacted 2h, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 1.8%;
The salpeter solution that the preparation mass percentage concentration is 30%;
The copper chloride active component solution that the preparation mass percentage concentration is 20%;
The potassium chloride compounding agent solution that the preparation mass percentage concentration is 30%;
The lanthanum chloride compounding agent solution that the preparation mass percentage concentration is 30%.
Use one-dimensional method the described sodium aluminate solution of 1000ml to be placed in to the stillpot of self-control belt stirrer, the salpeter solution 1040ml that to add gradually wherein mass percentage concentration be 30%, and turn on agitator stirred 2.0h to it and carry out precipitation reaction, reaction temperature is set in this reaction is 40 ℃, pH value is 6.5; Reaction finishes to be precipitated thing by filtration, utilizes deionized water to be washed to eluent to this sediment and stops for neutrality, obtains wet cake 840g.
Wet cake is added in the peptization still of making belt stirrer by oneself, and add wherein the deionized water 1260ml of 1.5 times of wet cake weight, the citric acid solution 11.6ml that the peptizing agent-mass percentage concentration that adds again wet cake weight 1.5% is 50%, under the high-speed stirred that is 450r/min at rotating speed, making beating peptization 1h, obtain sol solution 1620ml.
The lanthanum chloride compounding agent solution 1.1ml that the copper chloride active component solution 54ml that is 20% by the quality percentage composition, potassium chloride compounding agent solution 8ml that mass percentage concentration is 30% and mass percentage concentration are 30% joins in above-mentioned sol solution, add wherein organic expanding agent starch derivatives dextrin 4.2g (wet cake weight 0.5%) simultaneously, obtain the mixed liquid of peptization.
The mixed liquid 1200ml of above-mentioned peptization is sent in the spray shaping drying tower and carries out spray shaping, it is 500 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 150 ℃, guarantee the time of staying 6s of article shaped in described spray shaping drying tower, obtain microspherical catalyst parent after drying; Above-mentioned microspherical catalyst parent is carried out to roasting 2h under 650 ℃ and can obtain ethylene oxychlorination catalyst E.
In this catalyst, copper content is 5%, and potassium content is 1.5%, and lanthanum content is 0.1%, and alumina carrier content is 81.4%, and all the other are chlorion and impurity.
embodiment 6
Take the 1000g aluminium hydrate powder, it is joined in the sodium hydroxide solution that the 1100ml mass percentage concentration is 30%, set temperature is 105 ℃ and is reacted 2h, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 1.8%;
The salpeter solution that the preparation mass percentage concentration is 30%;
The copper chloride active component solution that the preparation mass percentage concentration is 20%;
The magnesium chloride compounding agent solution that the preparation mass percentage concentration is 30%;
The lanthanum chloride compounding agent solution that the preparation mass percentage concentration is 30%.
Use one-dimensional method the described sodium aluminate solution of 1000ml to be placed in to the stillpot of self-control belt stirrer, the salpeter solution 1040ml that to add gradually wherein mass percentage concentration be 30%, and turn on agitator stirred 2.0h to it and carry out precipitation reaction, reaction temperature is set in this reaction is 40 ℃, pH value is 6.5; Reaction finishes to be precipitated thing by filtration, utilizes deionized water to be washed to eluent to this sediment and stops for neutrality, obtains wet cake 840g.
Wet cake is added in the peptization still of making belt stirrer by oneself, and add wherein the deionized water 1260ml of 1.5 times of wet cake weight, the citric acid solution 9.3ml that the peptizing agent-mass percentage concentration that adds again wet cake weight 1.2% is 50%, under the high-speed stirred that is 450r/min at rotating speed, making beating peptization 1h, obtain sol solution 1610ml.
The lanthanum chloride compounding agent solution 4ml that the copper chloride active component solution 70ml that is 20% by the quality percentage composition, magnesium chloride compounding agent solution 8.4ml that mass percentage concentration is 30% and mass percentage concentration are 30% joins in above-mentioned sol solution, add wherein organic expanding agent starch derivatives dextrin 2.52g (wet cake weight 0.3%) simultaneously, obtain the mixed liquid of peptization.
The mixed liquid 1500ml of above-mentioned peptization is sent in the spray shaping drying tower and carries out spray shaping, it is 500 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 150 ℃, guarantee the time of staying 6s of article shaped in described spray shaping drying tower, obtain microspherical catalyst parent after drying; Above-mentioned microspherical catalyst parent is carried out to roasting 2h under 650 ℃ and can obtain ethylene oxychlorination catalyst F.
In this catalyst, copper content is 6.5%, and content of magnesium is 2.0%, and lanthanum content is 0.3%, and alumina carrier content is 91%, and all the other are chlorion and impurity.
embodiment product physico-chemical property test case
The present invention has also carried out the test of physicochemical properties to the ethylene oxychlorination catalyst prepared in embodiment 1～6, test result is shown in as shown in Table 1 below.
The physicochemical properties of table 1 catalyst
| Product | Catalyst A | Catalyst B | Catalyst C | Catalyst D | Catalyst E | Catalyst F |
| Outward appearance | The brown color microballoon | The brown color microballoon | The brown color microballoon | The brown color microballoon | The brown color microballoon | The brown color microballoon |
| Specific area/m 2·g -1 | 155 | 193 | 230 | 189 | 186 | 210 |
| Pore volume/mlg -1 | 0.43 | 0.59 | 0.60 | 0.51 | 0.52 | 0.56 |
| Bulk density/gml -1 | 1.15 | 0.96 | 0.97 | 0.97 | 1.02 | 0.99 |
| Particle mean size/μ m | 51 | 51 | 52 | 52 | 52 | 51 |
| Abrasion performance/%h -1 | ＜0.07 | ＜0.08 | ＜0.10 | ＜0.08 | ＜0.06 | ＜0.07 |
From above-mentioned data, compared to prior art, utilize the ethylene oxychlorination catalyst that the preparation method of microspherical ethylene oxychlorination catalyst of the present invention prepares to there is higher pore volume and specific area, although the amplitude of its increase is very not large, but for large-scale dichloroethanes production, because output is very large, can obtain high as far as possible dichloroethanes conversion ratio so increase a little the above-mentioned performance of ethylene oxychlorination catalyst, be also that economic worth is arranged very much.
the catalyst activity evaluation Example
The present invention also carries out activity rating to the above-mentioned catalyst A～F prepared, and this test is carried out in the small-sized fluidized bed reactor of 100ml, and step is as follows:
Test environment: the 100ml catalyst of packing in reactor, with after nitrogen replacement, be warming up to 220 ℃, then pass into successively hydrogen chloride, ethene and oxygen carry out catalytic reaction;
Reaction condition: 220 ± 5 ℃ of temperature, pressure 0.3 ± 0.01Mpa;
Material molar ratio: C
2h
4: HCl: O
2=1.04: 2: 0.57
The evaluating catalyst result is as shown in table 2.
Table 2 evaluating catalyst result
| Product | Catalyst A | Catalyst B | Catalyst C | Catalyst D | Catalyst E | Catalyst F |
| Reaction temperature/℃ | 220 | 220 | 219 | 219 | 218 | 217 |
| Reaction pressure/MPa | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| HCl conversion ratio/% | 99.54 | 99.72 | 99.94 | 99.89 | 99.63 | 99.82 |
| Dichloroethanes yield/gh-1 | 19.9 | 20.21 | 24.57 | 24.36 | 21.1 | 23.08 |
| Dichloroethanes purity/% | 99.59 | 99.64 | 99.91 | 99.83 | 99.63 | 99.78 |
| Tail gas CO2/% (v) | 0.91 | 0.86 | 0.62 | 0.69 | 0.89 | 0.83 |
| Tail gas CO/% (v) | 0.17 | 0.10 | 0.04 | 0.06 | 0.12 | 0.09 |
As can be seen from the above data, the catalyst that adopts the inventive method to make, because Active components distribution is even, specific area and pore volume are larger, and the interior diffusion of reaction molecular and external diffusion performance strengthen, so the hydrogen chloride conversion ratio obviously improves, CO in tail gas
2reach CO content and obviously reduce, yield and the purity of purpose product all are improved.
Although the present invention elaborates it by the specific embodiment; but; those skilled in the art should be understood that any form that does not exceed the claim protection domain made on this basis and the variation of details, all belong to invention which is intended to be protected.
Claims (9)
1. the preparation method of an ethylene oxychlorination catalyst, comprise the steps:
(a) aluminium hydrate powder is joined in sodium hydroxide solution, set temperature is 95～125 ℃ and is reacted, prepares the sodium aluminate solution that alundum (Al2O3) and NaOH percentage by weight are 1.15～2.25%;
The acid solution that the preparation mass percentage concentration is 25～40%;
Preparation active component solution and compounding agent solution;
(b) described sodium aluminate solution and described acid solution are mixed under stirring, reaction temperature is set is 30～70 ℃, pH value and be 5～9 is reacted, be precipitated after filtering thing, utilize deionized water to be washed to eluent described sediment and stop for neutrality, obtain wet cake;
(c) described wet cake is added in the peptization still, and add the deionized water that is equal to or greater than described wet cake weight, then add the peptizing agent of described wet cake weight 0.5～2.5%, the peptization of pulling an oar under the high-speed stirred that is 300～500r/min at rotating speed;
(d) active component solution and compounding agent solution are joined in the sol solution that step (c) makes, add respectively wherein organic expanding agent, the amount of described organic expanding agent is 0.1～0.5% of described wet cake weight, obtains the mixed liquid of peptization simultaneously;
(e) the mixed liquid of the described peptization after peptization is sent in the spray shaping drying tower and carried out spray shaping, it is 450～600 ℃ that described spray shaping drying tower hot blast inlet temperature is set, outlet temperature is 100～160 ℃, the time of staying 3～10s in described spray shaping drying tower, obtain microspherical catalyst parent after drying;
(f) the microspherical catalyst parent made in step (e) is carried out to roasting under 300～800 ℃ and prepare described ethylene oxychlorination catalyst;
Wherein, the described ethylene oxychlorination catalyst prepared, following component, consist of: at least one the 0.2～2wt% in copper 4～7.5wt%, magnesium and potassium, rare earth element 0.1～1.0wt%, gamma-aluminium oxide carrier 81.0～91.0wt%, surplus is chlorion and impurity.
2. preparation method according to claim 1, is characterized in that, the described reaction temperature in described step (b) is 40～50 ℃, and the reaction time is 1～2h.
3. preparation method according to claim 1, is characterized in that, the described pH value in described step (b) is 6.5～8.
4. preparation method according to claim 1, is characterized in that, the amount of the described deionized water added in described step (c) is 1～1.5 times of described wet cake weight.
5. preparation method according to claim 1, is characterized in that, the amount of the described peptizing agent added in described step (c) is 1.0～1.5% of described wet cake weight.
6. preparation method according to claim 1 or 5, is characterized in that, described peptizing agent is salpeter solution or the citric acid solution that mass percentage concentration is 30～50%.
7. preparation method according to claim 1, is characterized in that, making beating peptization 1～2h under the high-speed stirred that is 300～500r/min at rotating speed in described step (c).
8. preparation method according to claim 1, is characterized in that, described organic expanding agent is carboxymethyl cellulose, starch derivatives.
9. preparation method according to claim 1, is characterized in that, in described step (f) by the microspherical catalyst parent in 450～650 ℃ of lower roasting 2～4h.
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| CN100998942A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Ethylene oxychlorination catalyst and its preparation method and application |
| CN101351266A (en) * | 2005-11-14 | 2009-01-21 | 氧化乙烯公司 | Catalyst compositions and process for oxychlorination |
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| CN101351266A (en) * | 2005-11-14 | 2009-01-21 | 氧化乙烯公司 | Catalyst compositions and process for oxychlorination |
| CN100998942A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Ethylene oxychlorination catalyst and its preparation method and application |
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