CN102728390B - Method for extracting catalyst for 2,6-dimethylnaphthalene from coal tar - Google Patents

Method for extracting catalyst for 2,6-dimethylnaphthalene from coal tar Download PDF

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CN102728390B
CN102728390B CN201210239728.0A CN201210239728A CN102728390B CN 102728390 B CN102728390 B CN 102728390B CN 201210239728 A CN201210239728 A CN 201210239728A CN 102728390 B CN102728390 B CN 102728390B
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diatomite
solution
dimethylnaphthalene
catalyst
coal tar
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CN102728390A (en
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韩钊武
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Abstract

The invention relates to a method for extracting a catalyst for 2,6-dimethylnaphthalene from coal tar, belonging to the field of catalysis in chemical industry. The method comprises the following steps: washing kieselguhr which is used as a supporter with acid, carrying out activating treatment by vapor and roasting, dissolving Pt-containing reagent in a hydrochloric acid solution, and slowly and dropwisely adding the kieselguhr subjected to activating treatment; and standing the impregnant at room temperature over night, drying, cooling to room temperature, dropwisely adding a nickel-containing solution onto the kieselguhr, aging, drying, and reducing with hydrogen to obtain the composite catalyst. The kieselguhr subjected to acid washing is used as a supporter to support Pt and Ni so as to prepare the composite catalyst; and thus, the invention solves the problems of high catalyst carbon deposition amount, short service life and low catalytic activity in the isomerization process of extracting 2,6-dimethylnaphthalene from coal tar, increases the isomerization conversion rate and enhances the recovery rate of 2,6-dimethylnaphthalene extracted from coal tar.

Description

A kind of method of extracting 2,6-dimethylnaphthalene catalyst from coal tar
Technical field
The present invention relates to a kind of method of extracting 2,6-dimethylnaphthalene catalyst from coal tar, belong to chemical catalysis field.
Background technology
2,6-dimethylnaphthalene (2,6-DMN) be the important source material of synthetic naphthalene polymer, after its oxidation 2, the PEN (PEN) that 6-naphthalenedicarboxylic acid and ethylene glycol polymerization make is a kind of novel polyester-type material, its intensity, heat resistance, anti-flammability, all higher than PET, demonstrate the combination property more superior than PET at aspects such as packaging, electronic component, films, are a kind of novel functional high molecule materials.Along with the expansion of PEN range of application, 2,6-DMN is needed to increase gradually.
The producing of 2,6-DMN has synthetic method and conventionally taking coal tar as raw material direct extraction method.Synthetic method is taking toluene, n-butene, carbon monoxide etc. as raw material, synthesizes, a series of steps such as hydrogenation, dehydration, dehydrocyclization are poly-, finally separate, and make 2,6-DMN under catalyst existence condition.(white snowy peak, Wu Wei, Zhang Guoqiang .2, synthetic [J] of 6-dimethylnaphthalene. chemical and bonding .2000 (02): 76-78) taking coal tar as raw material direct extraction method, that coal tar obtains rich dimethylnaphthalene fraction by rectifying, through isomerization, absorption or coordination crystallization directly separate 2,6-DMN again.(.[J of resources and environment research institute of Japanese industry scientific and technical research institute]. petrochemical industry, 1997,26 (8): 575)
Dimethylnaphthalene isomerization is existing a large amount of report abroad, and because isomerization reaction is close with disproportionation process, therefore, in isomerization reaction, how improving isomerization reaction conversion ratio and reducing disproportionation is the key of isomerization reaction.Can accelerate reaction rate although improve temperature, to 1,6-DMN, 2, the equilibrium concentration impact of 6-DMN and 1,5-DMN is little, and temperature can be impelled the generation of disproportionation, the yield that reduces isomerization reaction, it is very important therefore selecting suitable catalyst.
Isomerization is produced the catalyst of 2,6-dimethylnaphthalene use generally taking y-type zeolite as main body, reduces side reaction and extending catalyst life-span, and require the thermodynamical equilibrium concentration of the content of 2,6-dimethylnaphthalene in raw material lower than it at zeolite surface impregnating metal; Now 2, the content of 6-DMN is increased to 5.1wt% from 1.6wt%, and the ratio in dimethylnaphthalene is increased to 15wt% from 3wt%; But y-type zeolite exists carbon deposition quantity of catalyst large, and service life is short, the problem that catalytic activity is low.Shu Geping mentions the content that increases aluminium in y-type zeolite in " producing the research of 2,6-dialkyl group naphthalene from coal tar " literary composition, then at surface impregnation nickel, can reduce side reaction, the extending catalyst life-span; But catalyst y-type zeolite needs presulfurization before using.At zeolite surface dipping Fe and Ni, catalyst activity, carbon deposition quantity have clear improvement, but the content of 2,6-DMN in dimethylnaphthalene is only increased to 12.59% from 10.80%, increases not obvious.(Shu Geping, Chen Peng, Du Shufeng. from coal tar, produce the research of 2,6-dialkyl group naphthalene. coal conversion, 1997 (20), 4:13-18).
Summary of the invention
The object of the invention is in order to solve in prior art 2, the problem that 6-DMN conversion ratio is not high, provides a kind of method of extracting 2,6-methyl naphthalene catalyst from coal tar.
The object of the invention is to be achieved through the following technical solutions:
One of the present invention is extracted the method for 2,6-dimethylnaphthalene catalyst from coal tar, and concrete preparation process is as follows:
Step 1, stir after diatomite is mixed with acid solution, filter, solid particle is dried, obtain the diatomite of pickling; The mass ratio of diatomite and acid solution is 1: 3~10;
Step 2, the diatomite of the pickling of step 1 gained is positioned in container, is warming up to after 300 DEG C~450 DEG C constant temperature activation, pass into steam, air-flow velocity is 3~6ml/min; Constant speed is warming up to 500~650 DEG C again, and roasting obtains activating diatomite;
Step 3, will be added drop-wise on the activation diatomite of step 2 gained containing Pt solution, leave standstill, dry at 80 DEG C~120 DEG C, be cooled to room temperature, obtain the diatomite of load containing Pt;
Step 4, by the load that is added drop-wise to step 3 gained containing Ni solution containing on the diatomite of Pt, leave standstill, dry at 100~150 DEG C, be cooled to after room temperature, obtain supporting Pt O 2diatomite with NiO;
Step 5, the diatomite of step 4 gained is positioned in reactor, passes into reducing gas, reduction obtains the tripolite composite catalyst of supporting Pt and Ni.
Acid strength described in step 1 is any one in sulfuric acid, nitric acid and the hydrochloric acid solution of 1~5mol/L;
Constant temperature soak time described in step 2 is not less than 1 hour; Roasting time is not less than 1 hour
Described in step 3 containing any one in Pt solution be 1~3mol/L platinum chloride solution, sulfurous acid platinum solution and platinum nitrate solution, any one in nickel sulfate solution that the solution containing nickel described in step 4 is 1~5mol/L, nickel nitrate solution, nickel bromide solution.
Reducing gas described in step 5 is any one in hydrogen, carbon monoxide, hydrogen sulfide, methane and sulfur monoxide.
Beneficial effect
1, one of the present invention is extracted to 2 from coal tar, the tripolite composite catalyst that 6-dimethylnaphthalene makes by the method for catalyst, be applied to the coal tar extraction 2 that Shu Geping proposes, in 6-dimethylnaphthalene method, 2, the content of 6-dimethylnaphthalene brings up to 28% by 1.8%, has compared with prior art improved twice.
2, one of the present invention is extracted the method for 2,6-dimethylnaphthalene catalyst from coal tar, simple to operate, not requirement of the concentration to 2,6-dimethylnaphthalene in raw material.
3, on laboratory room small-sized reaction unit, use this composite catalyst continuous operation checking embodiment 1 to obtain the catalytic capability of catalyst.The operating condition of technique is: controlled pressure 10MPa; 350 DEG C of temperature, air speed is 0.5h -1; Hydrogen flowing quantity is 800ml/min, and after continuous operation 3000h, beds pressure drop does not increase, and the catalyst drawing off is without caking phenomenon, and in coal tar dimethylnaphthalene cut 2,6-DMN content increases after tested, and the rate of recovery of dimethylnaphthalene is brought up to more than 96%.
Detailed description of the invention
Below in conjunction with embodiment, content of the present invention is described further.
Embodiment 1
Step 1, diatomite is joined in 3mol/L salpeter solution and to be mixed after, stir, be heated to 100 DEG C simultaneously, constant temperature stirs after one hour and is cooled to room temperature, filters, and solid particle is dried, and obtains the diatomite of pickling; The mass ratio of diatomite and acid solution is 1: 3;
Step 2, the diatomite of the pickling of step 1 gained is positioned in tube furnace, is warming up to after 300 DEG C of constant temperature activation 1h, pass into steam, air-flow velocity is 3ml/min, processes 6 hours.Rise to constant speed with 3 DEG C/min more again and be warming up to 500 DEG C, roasting 3h, obtains activating diatomite;
Step 3,10ml1mol/L platinum chloride solution is added drop-wise on the activation diatomite of step 2 gained, leaves standstill after 12 hours, dry at 80 DEG C, be cooled to room temperature, obtain the diatomite of load containing Pt;
Step 4,1mol/L nickel sulfate solution is added drop-wise to step 3 gained load containing on the diatomite of Pt, leave standstill after 12 hours, dry at 100 DEG C, be cooled to after room temperature, obtain supporting Pt O 2diatomite with NiO;
Step 5, the diatomite of step 4 gained is positioned in reactor, passes into hydrogen, heat to 60 DEG C, continue to purge 30min with 0.5MPa hydrogen, reduction obtains the tripolite composite catalyst of supporting Pt and Ni.
Taking 255~275 DEG C of cuts in 1000g coal tar distillation process as raw material, add 0.5g catalyst of the present invention, control 350 DEG C of reaction temperatures, hydrogen flowing quantity 800mL/h, in reactor, react 6h, through liquid chromatographic detection, 2,6-DMN content has brought up to 25%, 1,6-DMN and 1,5-DMN composition almost do not have, be transformed into 2,6-DMN completely.
Embodiment 2
Step 1, diatomite is joined in 2mol/L hydrochloric acid solution and to be mixed after, stir, be heated to 200 DEG C simultaneously, constant temperature is cooled to room temperature after stirring 2h, filters, and solid particle is dried, and obtains the diatomite of pickling; The mass ratio of diatomite and acid solution is 1: 10;
Step 2, the diatomite of the pickling of step 1 gained is positioned in tube furnace, is warming up to after 450 DEG C of constant temperature activation 2h, pass into steam, air-flow velocity is 6ml/min, processes 4 hours.Rise to constant speed with 3 DEG C/min more again and be warming up to 650 DEG C, roasting 2h, obtains activating diatomite;
Step 3,15ml2mol/L sulfurous acid platinum solution is added drop-wise on the activation diatomite of step 2 gained, leaves standstill after 12 hours, dry at 100 DEG C, be cooled to room temperature, obtain the diatomite of load containing Pt;
Step 4,3mol/L nickel nitrate solution is added drop-wise to step 3 gained load containing on the diatomite of Pt, leave standstill after 12 hours, dry at 150 DEG C, be cooled to after room temperature, obtain supporting Pt O 2diatomite with NiO;
Step 5, the diatomite of step 4 gained is positioned in reactor, passes into carbon monoxide, heat to 60 DEG C, continue to purge 30min with 0.5MPa carbon monoxide, reduction obtains the tripolite composite catalyst of supporting Pt and Ni.
Taking 255~275 DEG C of cuts in 1000g coal tar distillation process as raw material, add 0.5g catalyst of the present invention, control 350 DEG C of reaction temperatures, hydrogen flowing quantity 800mL/h, in reactor, react 6h, through liquid chromatographic detection, 2,6-DMN content has brought up to 29%, 1,6-DMN and 1,5-DMN composition almost do not have, be transformed into 2,6-DMN completely.
Embodiment 3
Step 1, diatomite is mixed with 3mol/L sulfuric acid after, stir, be heated to more than 150 DEG C simultaneously, constant temperature stirs after 3h and is cooled to room temperature, filters, and solid particle is dried, and obtains the diatomite of pickling; The mass ratio of diatomite and acid solution is 1: 8;
Step 2, the diatomite of the pickling of step 1 gained is positioned in Muffle furnace, is warming up to after 380 DEG C of constant temperature activation, pass into steam, air-flow velocity is 4ml/min; Constant speed is warming up to 580 DEG C again, and roasting 4h obtains activating diatomite;
Step 3,3mol/L platinum nitrate solution is added drop-wise on the activation diatomite of step 2 gained, leaves standstill after 24 hours, dry at 100 DEG C, be cooled to room temperature, obtain the diatomite of load containing Pt;
Step 4,4mol/L nickel bromide solution is added drop-wise to step 3 gained load containing on the diatomite of Pt, leave standstill after 24 hours, dry at 120 DEG C, be cooled to after room temperature, obtain supporting Pt O 2diatomite with NiO;
Step 5, the diatomite of step 4 gained is positioned in reactor, passes into hydrogen sulfide, heat to 60 DEG C, continue to purge 30min with 0.5MPa hydrogen sulfide, reduction obtains the tripolite composite catalyst of supporting Pt and Ni.
Taking 255~275 DEG C of cuts in 1000g coal tar distillation process as raw material, add 0.5g catalyst of the present invention, control 350 DEG C of reaction temperatures, hydrogen flowing quantity 800mL/h, in reactor, react 6h, through liquid chromatographic detection, 2,6-DMN content has brought up to 23%, 1,6-DMN and 1,5-DMN composition almost do not have, be transformed into 2,6-DMN completely.
Embodiment 4
Step 1, diatomite is mixed with 3mol/L hydrochloric acid solution after, stir, be heated to more than 150 DEG C simultaneously, constant temperature stirs after 3h and is cooled to room temperature, filters, and solid particle is dried, and obtains the diatomite of pickling; The mass ratio of diatomite and acid solution is 1: 5;
Step 2, the diatomite of the pickling of step 1 gained is positioned in container, is warming up to after 400 DEG C of constant temperature activation, pass into steam, air-flow velocity is 5ml/min; Constant speed is warming up to 600 DEG C again, and roasting 2h obtains activating diatomite;
Step 3,5mol/L platinum nitrate solution is added drop-wise on the activation diatomite of step 2 gained, leaves standstill after 12 hours, dry at 90 DEG C, be cooled to room temperature, obtain the diatomite of load containing Pt;
Step 4,2mol/L nickel sulfate solution is added drop-wise to step 3 gained load containing on the diatomite of Pt, leave standstill after 36 hours, dry at 120 DEG C, be cooled to after room temperature, obtain supporting Pt O 2diatomite with NiO;
Step 5, the diatomite of step 4 gained is positioned in reactor, passes into methane, heat to 60 DEG C, continue to purge 30min with 0.5MPa methane, reduction obtains the tripolite composite catalyst of supporting Pt and Ni.
Taking 255~275 DEG C of cuts in 1000g coal tar distillation process as raw material, add 0.5g catalyst of the present invention, control 350 DEG C of reaction temperatures, hydrogen flowing quantity 800mL/h, in reactor, react 6h, through liquid chromatographic detection, 2,6-DMN content has brought up to 30%, 1,6-DMN and 1,5-DMN composition almost do not have, be transformed into 2,6-DMN completely.
Embodiment 5
Step 1, diatomite is mixed with 3mol/L salpeter solution after, stir, be heated to 200 DEG C simultaneously, constant temperature stirs after 2 hours and is cooled to room temperature, filters, and solid particle is dried, and obtains the diatomite of pickling; The mass ratio of diatomite and acid solution is 1: 5;
Step 2, the diatomite of the pickling of step 1 gained is positioned in container, is warming up to after 420 DEG C of constant temperature activation, pass into steam, air-flow velocity is 5ml/min; Constant speed is warming up to 600 DEG C again, and roasting 1h obtains activating diatomite;
Step 3,2mol/L platinum chloride solution is added drop-wise on the activation diatomite of step 2 gained, leaves standstill after 24 hours, dry at 120 DEG C, be cooled to room temperature, obtain the diatomite of load containing Pt;
Step 4,3mol/L nickel nitrate solution is added drop-wise to step 3 gained load containing on the diatomite of Pt, leave standstill after 24 hours, dry at 150 DEG C, be cooled to after room temperature, obtain supporting Pt O 2diatomite with NiO;
Step 5, the diatomite of step 4 gained is positioned in reactor, passes into sulfur monoxide, heat to 60 DEG C, continue to purge 30min with 0.5MPa sulfur monoxide, reduction obtains the tripolite composite catalyst of supporting Pt and Ni.
Taking 255~275 DEG C of cuts in 1000g coal tar distillation process as raw material, add 0.5g catalyst of the present invention, control 350 DEG C of reaction temperatures, hydrogen flowing quantity 800mL/h, in reactor, react 6h, through liquid chromatographic detection, 2,6-DMN content has brought up to 28%, 1,6-DMN and 1,5-DMN composition almost do not have, be transformed into 2,6-DMN completely.

Claims (4)

1. one kind is extracted the method for 2,6-dimethylnaphthalene catalyst from coal tar, it is characterized in that: concrete preparation process is as follows:
Step 1, diatomite is mixed with acid solution after, stir, filter, solid particle is dried, obtain the diatomite of pickling; The mass ratio of diatomite and acid solution is 1: 3~10;
Step 2, the diatomite of the pickling of step 1 gained is positioned in container, is warming up to after 300 DEG C~450 DEG C constant temperature activation, pass into steam, air-flow velocity is 3~6ml/min; Constant speed is warming up to 500~650 DEG C again, and roasting obtains activating diatomite;
Step 3, will be added drop-wise on the activation diatomite of step 2 gained containing Pt solution, leave standstill, dry at 80 DEG C~120 DEG C, be cooled to room temperature, obtain the diatomite of load containing Pt;
Step 4, by the load that is added drop-wise to step 3 gained containing Ni solution containing on the diatomite of Pt, leave standstill, dry at 100~150 DEG C, be cooled to after room temperature, obtain supporting Pt O 2diatomite with NiO;
Step 5, the diatomite of step 4 gained is positioned in reactor, passes into reducing gas, reduction obtains the tripolite composite catalyst of supporting Pt and Ni;
Wherein the acid solution described in step 1 is any one in sulfuric acid, nitric acid and hydrochloric acid solution; Described acid strength is 1~5mol/L; Reducing gas described in step 5 is any one in hydrogen, carbon monoxide, hydrogen sulfide, methane and sulfur monoxide.
2. one as claimed in claim 1 is extracted the method for 2,6-dimethylnaphthalene catalyst from coal tar, it is characterized in that: the constant temperature soak time described in step 2 is not less than 1 hour; Roasting time is not less than 1 hour.
3. one as claimed in claim 1 is extracted the method for 2,6-dimethylnaphthalene catalyst from coal tar, it is characterized in that: any one in the platinum chloride solution, sulfurous acid platinum solution and the platinum nitrate solution that are 1~3mol/L containing Pt solution described in step 3.
4. one as claimed in claim 1 is extracted the method for 2,6-dimethylnaphthalene catalyst from coal tar, it is characterized in that: any one in nickel sulfate solution that the solution containing nickel described in step 4 is 1~5mol/L, nickel nitrate solution, nickel bromide solution.
CN201210239728.0A 2012-07-12 2012-07-12 Method for extracting catalyst for 2,6-dimethylnaphthalene from coal tar Expired - Fee Related CN102728390B (en)

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