CN111905746B - Refined catalyst of cyclic formaldehyde derivative and application thereof - Google Patents
Refined catalyst of cyclic formaldehyde derivative and application thereof Download PDFInfo
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
The present disclosure provides a refined catalyst of cyclic derivatives of formaldehyde, comprising an acidic active component and a hydrogenation active component; the acid active component is used for carrying out acid catalysis on impurities in a trioxymethylene product or a dioxypentacyclic product so as to decompose methylal or formaldehyde polymer into formaldehyde or methanol; the hydrogenation active component is used for carrying out catalytic hydrofining on impurities in a trioxymethylene product or a dioxolane product so as to catalytically convert formaldehyde, formic acid or methyl formate into methanol. The present disclosure also provides a method of refining cyclic derivatives of formaldehyde. The method can be applied to the refining processes of aldehyde removal, deacidification and degreasing for preparing the cyclic formaldehyde derivative by using formaldehyde substances as raw materials.
Description
Technical Field
The disclosure relates to the field of catalysts, and in particular relates to a refined catalyst of cyclic formaldehyde derivatives and application thereof.
Background
Polyoxymethylene (POM), also known as acetal resin and polyoxymethylene, is a thermoplastic engineering plastic with excellent comprehensive properties, is one of five engineering plastics, is an engineering plastic with mechanical properties closest to metal materials in engineering plastics, and is known as "super steel" or "stainless steel". The key monomers for the production of polyoxymethylene are Trioxymethylene (TOX) and Dioxolane (DOL), the purity of which directly affects the properties of the polymer, and therefore requires less than 100ppm total impurities.
The traditional trioxymethylene synthesis method takes 50-65% high-concentration formaldehyde as a raw material to synthesize trioxymethylene under the action of an acid catalyst. The reaction is a rapid reversible reaction, but the reaction equilibrium constant is small, the conversion rate of formaldehyde is low, and only trioxymethylene with the equilibrium composition of about 3% is obtained in the reaction liquid, so that the reaction conversion rate is improved by adopting reaction rectification. At 100kPa, trioxymethylene, water and formaldehyde can form the lowest azeotrope, and the azeotropic composition is 69.5wt% of trioxymethylene, 5.4wt% of formaldehyde and 25.1wt% of water. In the azeotropic distillation process, an entrainer is added to ensure that trioxymethylene, water, formaldehyde and the entrainer form a new minimum azeotrope, when the azeotropic distillation is carried out, the new azeotrope is evaporated out at the top of the tower, and the solution with higher purity of trioxymethylene is obtained at the bottom of the tower. The commonly used entrainers are benzene and dichloroethane, and the entrainer is recycled in production. Extracting and rectifying to break through azeotropic composition to concentrate the content of trioxymethylene, and refining by dealcoholizing, extracting agent removal and other working sections to obtain trioxymethylene.
The traditional production process of the dioxolane takes 60 percent formaldehyde water solution or paraformaldehyde and ethylene glycol as raw materials, ion exchange resin or sulfuric acid as a catalyst, and normal pressure reaction is carried out at 90-110 ℃. Distilling off azeotrope from the top of the distillation column, salting out with sodium chloride and dehydrating with anhydrous calcium chloride, and rectifying and purifying to obtain the final product. In the process, the conversion rate of raw materials is low, and a large amount of unreacted materials are discharged from the reaction kettle, so that the environmental pollution and the raw material waste are caused; meanwhile, the refining route of the crude product is complicated, the occupied equipment is more, and the equipment investment and energy consumption are increased; in addition, the raw material paraformaldehyde needs to be prepared from a formaldehyde solution through the working procedures of concentration, polymerization, drying, aging and the like, so that the equipment investment is high, and the energy consumption is high.
However, a series of side reactions occur during the synthesis of trioxymethylene and dioxolane, regardless of the catalytic system employed. The most important of these is the disproportionation of formaldehyde (Cannizzaro) to methanol and formic acid.
The generated formic acid is corrosive, and the increase of the content of the formic acid can corrode equipment and influence the service life of the equipment. The methanol and the formic acid are further esterified to generate methyl formate under the action of a catalyst.
Formaldehyde may also form methyl formate in one step by the Tischenko reaction.
At the same time, formic acid, methyl formate, methanol and the like generated by side reaction, unreacted formaldehyde, water brought by raw materials and formaldehyde polymer (R1-O- (CH) generated by self-polymerization of formaldehyde 2 O) n-R2, wherein n is an integer of 0-50, R1 and R2 are C1-C5 alkyl, hydrogen, the formaldehyde polymer is hemiacetal, acetal of formaldehyde), and the product dioxolane or trioxymethylene, plus the multiple azeotropes (trioxymethylene and water, trioxymethylene, formaldehyde and water, dioxolane and water, etc.), greatly increase the separation difficulty. Meanwhile, due to the fact that the local concentration of formaldehyde in the separation unit is too high, formaldehyde polymers are easily formed, and therefore pipelines of the rectifying tower are blocked.
Disclosure of Invention
In order to solve at least one of the above technical problems, the present disclosure provides a catalyst for refining cyclic derivatives of formaldehyde and use thereof. According to one aspect of the present disclosure, a refined catalyst for cyclic derivatives of formaldehyde comprises an acidic active component and a hydrogenation active component; the acid active component is used for carrying out acid catalysis on impurities in a trioxymethylene product or a dioxypentacyclic product so as to decompose methylal or formaldehyde polymer into formaldehyde or methanol; the hydrogenation active component; used for catalytic hydrofining of impurities in the trioxymethylene product or the dioxolane product to catalytically convert formaldehyde, formic acid or methyl formate into methanol.
According to at least one embodiment of the present disclosure, the hydrogenation active component comprises a main catalyst component of one or more of Cu, ni and Pt, a promoter component of one or more of Zn, mg and Co, and a carrier of Al 2 O 3 、SiO 2 One or more components of active carbon and molecular sieve.
According to at least one embodiment of the present disclosure, the hydrogenation active component is a Cu-based catalyst system, and the catalyst system comprises Cu as a main catalyst component, zn or Mg or Co as a Co-catalyst component, and Al as a carrier 2 O 3 、SiO 2 One or more components of active carbon and molecular sieve.
According to at least one embodiment of the present disclosure, the hydrogenation active component is a Pt-based catalyst system, and the catalyst system comprises Pt as a main catalyst component, zn as a cocatalyst component, and Al as a carrier 2 O 3 、SiO 2 Activated carbon and molecular sieve.
According to at least one embodiment of the present disclosure, the acidic active component is Al 2 O 3 SiO carrying an acidic substance 2 And one or more components of a molecular sieve.
According to at least one embodiment of the present disclosure, the molecular sieve is a ZSM-5 molecular sieve or a Beta molecular sieve.
According to at least one embodiment of the present disclosure, the mass of the hydrogenation active component accounts for 10 to 70% of the total mass of the catalyst.
According to at least one embodiment of the present disclosure, the mass of the acidic active component is 0.1 to 10% of the total mass of the catalyst and does not cause decomposition of the cyclic derivatives of formaldehyde.
According to at least one embodiment of the present disclosure, the hydrogenation active component is loaded on the acidic active component, or the hydrogenation active component and the acidic active component are mechanically mixed and then tableted, or the hydrogenation active component and the acidic active component are mechanically mixed and then added with a binder to be extruded into strips.
According to one aspect of the present disclosure, a method of refining a cyclic derivative of formaldehyde comprises the steps of: the impurities in the trioxymethylene product or the dioxypentacyclic product are subjected to acid catalysis and hydrogenation catalytic refining by adopting a fixed bed reactor under the condition of a refining catalyst to remove formaldehyde, formic acid and methyl formate contained in the trioxymethylene product or the dioxypentacyclic product.
According to at least one embodiment of the present disclosure, the process conditions of the acid catalysis and the hydrogenation catalytic refining are as follows: the reaction temperature is 80-120 ℃; the reaction pressure is 0.2-2Mpa; the liquid space velocity is 0.5-5h -1 The space velocity of hydrogen is 10-80h -1 。
According to at least one embodiment of the present disclosure, the reaction temperature is 120 ℃; the reaction pressure is 2Mpa; the reaction space velocity is 1h -1 The space velocity of hydrogen is 50h -1 。
According to one aspect of the present disclosure, a method for preparing a refined catalyst of a cyclic derivative of formaldehyde, in which a hydrogenation active component is supported on the acidic active component, comprises the steps of:
a. preparing a mixed aqueous solution of copper nitrate, zinc nitrate and aluminum nitrate, and recording the mixed aqueous solution as a solution I; b. putting a commercial ZSM-5 molecular sieve into a hollow mesh container, soaking the mesh container in the solution I at 70 ℃ for 1h, and stirring the solution in the hollow part to ensure that the solution is uniformly soaked; c. after the impregnation is finished, dripping the impregnation liquid in the impregnation liquid steam, washing, filtering, drying at 40 ℃ for 1697 h, drying at 120 ℃ for 8h, roasting at 300 ℃ for 2h by temperature programming and sectional roasting, and roasting at 500 ℃ for 4h to obtain the copper-zinc-aluminum supported catalyst.
According to one aspect of the present disclosure, a method for preparing a refined catalyst of cyclic derivatives of formaldehyde, wherein a hydrogenation active component and the acidic active component are mechanically mixed and then tableted, comprises the following steps:
a. preparing a mixed aqueous solution of copper nitrate, zinc nitrate and aluminum nitrate, and recording the mixed aqueous solution as a solution I; b. preparation of NaHCO 3 The aqueous solution is marked as solution II; c. slowly dripping the solution II into the solution I at the constant temperature of 60-80 ℃ and the stirring speed of 200-400rpm, aging, filtering, and drying a filter cakeTo prepare the copper-zinc-aluminum powder catalyst; d. weighing a certain mass of the copper-zinc-aluminum powder catalyst and SiO loaded with sulfonic acid 2 Mixing with graphite, and tabletting; and preparing the tabletting catalyst.
According to at least one embodiment of the present disclosure, in the step a, the mixed aqueous solution of the copper nitrate, the zinc nitrate and the aluminum nitrate is prepared by respectively weighing a certain mass of Cu (NO) 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in quantitative deionized water.
According to at least one embodiment of the present disclosure, in the step c, the dropping speed of the solution ii into the solution i is 0.5 drops/second, when the pH =7.00, the dropping of the solution ii is stopped, the solution is aged for 1 hour under the same temperature and stirring conditions, after the aging is finished, the solution is filtered, the filter cake is repeatedly washed with deionized water and filtered until the filtrate is colorless, and the obtained filter cake is dried at 120 ℃ for 6 hours.
According to at least one embodiment of the present disclosure, in the step d, the copper-zinc-aluminum powder catalyst and the SiO supported sulfonic acid are mixed and stirred separately 2 And grinding graphite to 100 mesh or less.
According to one aspect of the present disclosure, a method for preparing a refined catalyst of cyclic formaldehyde derivatives, wherein a hydrogenation active component and an acidic active component are mechanically mixed and then added with a binder for extrusion molding, comprises the following steps:
a. preparing a mixed aqueous solution of copper nitrate, zinc nitrate and aluminum nitrate, and recording the mixed aqueous solution as a solution I; b. preparation of NaHCO 3 The aqueous solution is marked as solution II; c. slowly dripping the solution II into the solution I at the constant temperature of 60-80 ℃ and the stirring speed of 200-400rpm, aging, filtering, and drying a filter cake to obtain the copper-zinc-aluminum powder catalyst; d. weighing a certain mass of the copper-zinc-aluminum powder catalyst, a ZSM-5 molecular sieve and methyl cellulose, adding the mixture into a kneader, mixing and stirring for 5-15min to obtain a mixture, adding a binder alumina sol into the mixture, kneading for 5-15min, and adding deionized water to the mixtureThe material is suitable for forming, continuously kneading for 10-20min, extruding and forming, drying and roasting to prepare the copper-ZSM-5 forming catalyst.
According to at least one embodiment of the present disclosure, in the step a, the mixed aqueous solution of the copper nitrate, the zinc nitrate and the aluminum nitrate is prepared by respectively weighing a certain mass of Cu (NO) 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in quantitative deionized water.
According to at least one embodiment of the present disclosure, in the step c, the dropping speed of the solution ii into the solution i is 0.5 drops/second, when the pH =7.00, the dropping of the solution ii is stopped, the solution is aged for 1 hour under the same temperature and stirring conditions, after the aging is finished, the solution is filtered, the filter cake is repeatedly washed with deionized water and filtered until the filtrate is colorless, and the obtained filter cake is dried at 120 ℃ for 6 hours.
According to at least one embodiment of the present disclosure, in the step d, the copper-zinc-aluminum powder catalyst and the ZSM-5 molecular sieve are respectively ground to 100 mesh or less before mixing and stirring.
According to at least one embodiment of the present disclosure, in the step d, after the extrusion molding, the molded catalyst is dried at 120 ℃ for 6 hours and then calcined at 350 ℃ for 2 hours.
The method can be applied to the refining processes of aldehyde removal, deacidification and degreasing for preparing the cyclic formaldehyde derivative by using formaldehyde substances as raw materials.
Detailed Description
The present disclosure will be described in further detail with reference to embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure.
It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. The present disclosure will be described in detail below by way of embodiments.
Example 1
The present disclosure provides a refined catalyst of cyclic derivatives of formaldehyde, comprising an acidic active component and a hydrogenation active component; the acid active component is used for carrying out acid catalysis on impurities in a trioxymethylene product or a dioxypentacyclic product so as to decompose methylal or formaldehyde polymer into formaldehyde or methanol; the hydrogenation active component; used for catalytic hydrofining of impurities in the trioxymethylene product or the dioxolane product to catalytically convert formaldehyde, formic acid or methyl formate into methanol.
The refining catalyst disclosed by the invention has double functions of hydrogenation and acid catalysis, and the acid catalysis function enables methylal and formaldehyde polymers to be decomposed into formaldehyde or methanol and the like:
R1-O-(CH 2 O)n-R2+H 2 O→nCH 2 O+R1OH+R2OH
the hydrogenation function can be used for catalytically converting formaldehyde, formic acid, methyl formate and the like into methanol:
CH 2 O+H 2 →CH 3 OH
HCOOH+H 2 →CH 3 OH
HCOOCH 3 +H 2 →CH 3 OH
the hydrogenation function can also make formaldehyde, formic acid, methyl formate and the like and water perform catalytic conversion:
CH 2 O+H 2 O→CO 2 +H 2
HCOOH→CO 2 +H 2
according to at least one embodiment of the present disclosure, the hydrogenation active component comprises a main catalyst component of one or more of Cu, ni and Pt, a promoter component of one or more of Zn, mg and Co, and a carrier of Al 2 O 3 、SiO 2 Activated carbon and molecular sieve.
According to at least one embodiment of the present disclosure, the hydrogenation active component is a Cu-based catalyst system, and the catalyst system includes a main catalyst component of Cu, a Co-catalyst component of Zn or Mg or Co, and a carrier of Al 2 O 3 、SiO 2 One or more components of active carbon and molecular sieve.
According toIn at least one embodiment of the present disclosure, the hydrogenation active component is a Pt-based catalyst system, and the catalyst system includes Pt as a main catalyst component, zn as a cocatalyst component, and Al as a carrier 2 O 3 、SiO 2 Activated carbon and molecular sieve.
According to at least one embodiment of the present disclosure, the acidic active component is Al 2 O 3 SiO carrying an acidic substance 2 Molecular sieve, or one or more components of molecular sieve.
According to at least one embodiment of the present disclosure, the molecular sieve is a ZSM-5 molecular sieve or a Beta molecular sieve.
According to at least one embodiment of the present disclosure, the mass of the hydrogenation active component accounts for 10 to 70% of the total mass of the catalyst.
According to at least one embodiment of the present disclosure, the mass of the acidic active component is 0.1 to 10% of the total mass of the catalyst and does not cause decomposition of the cyclic derivatives of formaldehyde.
EXAMPLE 2 extrusion-molded refined catalyst prepared by coprecipitation method
The present disclosure also provides a method for preparing the refined catalyst of example 1, wherein the hydrogenation active component is mechanically mixed with the acidic active component, and then added with a binder to be formed by extrusion molding, comprising the steps of:
weighing 118g of Cu (NO) 3 ) 2 ·3H 2 O、30g Zn(NO 3 ) 2 ·6H 2 O and 25g Al (NO) 3 ) 3 ·9H 2 Dissolving O in quantitative deionized water, preparing 350mL of copper-zinc-aluminum mixed nitrate aqueous solution, and marking as solution I; 250g of NaHCO are weighed 3 Dissolving in quantitative deionized water to prepare 2L NaHCO 3 The aqueous solution is marked as solution II; slowly dripping the solution II into the mixed solution I at the constant temperature of 70 ℃ and the stirring speed of 300rpm, wherein the dripping speed is about 0.5 droplet/second, stopping dripping the solution II when the pH of the mixed solution is =7.00, the using amount of the solution II is 1150mL, and aging for 1h under the same temperature and stirring conditions; filtering the solution after aging, repeatedly washing the filter cake with deionized water, and filtering until the filtrate is colorless to obtainThe filter cake is dried for 6 hours at 120 ℃ to obtain the copper-zinc-aluminum powder catalyst.
Grinding the copper-zinc-aluminum powder catalyst to be below 100 meshes, and weighing 60.00g of the powder catalyst in a kneader; weighing 0.875g of methyl cellulose in the operating state of a kneader, slowly adding the methyl cellulose into the kneader, mixing and stirring for 10min, slowly adding a binder alumina sol into the mixed powder, stopping adding the binder when the material is in a slightly wet state, kneading for 10min, adding 1.20g of deionized water until the material is suitable for forming, continuing kneading for 15min, extruding and forming, wherein the specification of a die is 2 x 2mm; drying the formed catalyst at 120 ℃ for 6h, then roasting at 350 ℃ for 2h, and adopting 0.5mol/L NH 4 NO 3 Ion exchange is carried out at 70 ℃ and roasting is carried out for 5h at 350 ℃. To obtain the copper-zinc-aluminum coprecipitation copper-zinc-aluminum type refined catalyst 1.
The hydrogenation active component of the catalyst is Cu, the auxiliary agent is ZnO, and the acidic active component is Al 2 O 3 The forming mode is a strip extruding method.
EXAMPLE 3 refined catalyst prepared by Co-impregnation
The present disclosure also provides a preparation method of the refined catalyst of example 1, wherein the hydrogenation active component is supported on the acidic active component, comprising the steps of: 157g of Ni (NO) are weighed 3 ) 2 ·6H 2 O、66g Mg(NO 3 ) 2 ·6H 2 Dissolving O in quantitative deionized water, and preparing 250mL of nickel-magnesium mixed nitrate impregnation solution, and marking as solution I; weighing 40.00g of 1100 ℃ roasted alumina microsphere carrier with the diameter of 4mm, placing the alumina microsphere carrier into a hollow mesh container, soaking the mesh container in the solution I at 70 ℃ for 1h, stirring the solution at the hollow part to ensure uniform soaking, dripping the soaking solution into soaking solution steam after the soaking is finished, drying 1693 ℃ after washing and suction filtration for 1697 h, drying at 120 ℃ for 8h, roasting at 300 ℃ for 2h by programmed heating and sectional roasting at 500 ℃ for 4h to obtain the Ni-Mg-Al co-impregnated supported refined catalyst 2.
The hydrogenation active component of the catalyst is Ni, the auxiliary agent is MgO, and the acidic active component is Al 2 O 3 。
EXAMPLE 4 refined catalyst prepared by Co-impregnation
The present disclosure also provides a preparation method of the refined catalyst of example 1, wherein the hydrogenation active component is supported on the acidic active component, comprising the steps of: a. preparing a mixed aqueous solution of copper nitrate, zinc nitrate and aluminum nitrate, and recording the mixed aqueous solution as a solution I; b. putting a commercial ZSM-5 molecular sieve into a hollow mesh container, soaking the mesh container in the solution I at 70 ℃ for 1h, and stirring the solution in the hollow part to ensure that the solution is uniformly soaked; c. after the impregnation is finished, dripping the impregnation liquid in the impregnation liquid steam, washing, filtering, drying at 40 ℃ for 1697 h, drying at 120 ℃ for 8h, roasting at 300 ℃ for 2h by temperature programming and sectional roasting, and roasting at 500 ℃ for 4h to obtain the copper-zinc-aluminum supported catalyst 3.
The hydrogenation active component of the catalyst is Cu, the auxiliary agent is ZnO, and the acidic active component is ZSM-5 molecular sieve.
EXAMPLE 5 refined catalyst prepared by stepwise impregnation
A step-by-step impregnation method: with 40g of H 2 PtCI 6 And 132mL of distilled water were added to prepare a platinum salt solution, and 20g of Zn (NO) was added 3 ) 2 ·6H 2 Preparing zinc salt solution by using O and 80mL of distilled water; adding ZSM-5 molded porous microspheres with the diameter of 2mm subjected to equal volume treatment into a 100mL beaker, dropwise adding a platinum salt solution while stirring, dropwise adding a zinc salt solution while stirring, and sealing and standing for 24 hours; finally, drying at 110 ℃ for 24h with 1mol/L NH 4 NO 3 Ion exchange is carried out at 80 ℃, the temperature is raised from 100.0 ℃ to 550.0 ℃ in a muffle furnace at the temperature rise rate of 1.5 ℃/min, and the platinum-zinc stepwise impregnated supported refined catalyst 4 is obtained after constant-temperature roasting for 4 hours.
The hydrogenation active component of the catalyst is Pt, the auxiliary agent is ZnO, and the acidic active component is ZSM-5 molecular sieve.
EXAMPLE 6 tabletting-shaped purified catalyst prepared by coprecipitation method
The disclosure also provides a method for preparing the refined catalyst of example 1, wherein the hydrogenation active component and the acidic active component are mechanically mixed and then tableted to form the refined catalyst, comprising the following steps:
a. preparing copper nitrate and zinc nitrateA mixed aqueous solution of salt and aluminum nitrate is marked as a solution I; b. preparation of NaHCO 3 The aqueous solution is marked as solution II; c. slowly dripping the solution II into the solution I at the constant temperature of 60-80 ℃ and the stirring speed of 200-400rpm, aging, filtering, and drying a filter cake to obtain the copper-zinc-aluminum powder catalyst; d. weighing a certain mass of the copper-zinc-aluminum powder catalyst and SiO loaded with sulfonic acid 2 Mixing with graphite, and tabletting; thus, a tableting-molded refined catalyst 5 was obtained.
According to at least one embodiment of the present disclosure, in the step a, the mixed aqueous solution of the copper nitrate, the zinc nitrate and the aluminum nitrate is prepared by respectively weighing a certain mass of Cu (NO) 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in quantitative deionized water.
According to at least one embodiment of the present disclosure, in the step c, the dropping speed of the solution ii into the solution i is 0.5 drops/second, when the pH =7.00, the dropping of the solution ii is stopped, the solution is aged for 1 hour under the same temperature and stirring conditions, after the aging is finished, the solution is filtered, the filter cake is repeatedly washed with deionized water and filtered until the filtrate is colorless, and the obtained filter cake is dried at 120 ℃ for 6 hours.
According to at least one embodiment of the present disclosure, in the step d, the copper-zinc-aluminum powder catalyst and the SiO supported sulfonic acid are mixed and stirred separately 2 And grinding the graphite to below 100 meshes.
The hydrogenation active component of the catalyst is Cu, the auxiliary agent is ZnO, and the acidic active component is SiO loaded with sulfonic acid 2 。
EXAMPLE 7 tabletting-Forming purified catalyst prepared by mechanical mixing
20g of activated Beta molecular sieve, 120g of CuCO 3 And 70g CoCO 3 Uniformly mixing, grinding and sieving to 300 meshes, then roasting at 350 ℃ for 8h to obtain CuO-CoO/Beta activated powder, adding graphite, tabletting and molding to obtain the columnar mechanically mixed CuO-CoO/Beta refined catalyst 6 with the diameter of 4mm and the length of 3 mm.
The hydrogenation active component of the catalyst is Cu, the auxiliary agent is CoO, and the acidic active component is a Beta molecular sieve.
EXAMPLE 8 purification of concentrated product of trioxymethylene Synthesis
1500.0kg of 65% formaldehyde was weighed and added to a 2.5L single-neck round-bottom flask, 50g of a resin catalyst was added to the reactor at a reaction temperature of 105 ℃ and a fraction at the outlet temperature of the reactor of 90 to 95 ℃ was collected to obtain a cyclized reaction product. Rectifying the reaction fraction (cyclization reaction product) to obtain a concentrated trioxymethylene mixture, wherein the reflux ratio is 4:1, the 95-100 ℃ overhead fraction was collected and had the composition shown in table 1 below. The refined catalyst 1 is loaded into a fixed bed refining reactor, and reduction pretreatment is carried out on the catalyst under the following reduction conditions: 230 ℃, 0.5Mpa and 120h of hydrogen space velocity -1 Space velocity of nitrogen 480h -1 。
Then refining the concentrated trioxymethylene mixture by using a refining catalyst 1, wherein the process conditions are as follows: the reaction pressure is 2.0MPa, the reaction temperature is 120 ℃, and the liquid space velocity is 1.0h -1 Space velocity of hydrogen gas of 50h -1 . The composition and distribution of the main materials before and after refining are shown in Table 1.
TABLE 1 trioxymethylene cyclization reaction product, concentrate and refined product composition
As can be seen from table 1, methyl Formate (MF), formaldehyde (HCHO) and formic acid (HCOOH) after purification are hydrorefined into methanol under the action of a catalyst, and methylal and formaldehyde polymer are firstly depolymerized into methanol and formaldehyde under the action of a catalyst and then hydrorefined into methanol, so that the impurity composition of the trioxymethylene reactant concentrated mixture is changed from 7 to 2.
EXAMPLE 9 purification of crude Melaldehyde Synthesis product
A concentrated trioxymethylene mixture was prepared as in example 8, followed by addition of benzene as an extractant, separation to obtain a trioxymethylene-rich benzene phase, and rectification to separate benzene to obtain trioxymethylene with a small amount of impurities, the composition of which is shown in Table 2.
The refined catalyst 2 is loaded into a fixed bed refining reactor, and reduction pretreatment is carried out on the catalyst under the following reduction conditions: 200 ℃, 0.3Mpa and the space velocity of hydrogen gas of 50h -1 And the space velocity of nitrogen is 200h -1 。
Then refining the concentrated trioxymethylene mixture by adopting a refining catalyst 2, wherein the process conditions are as follows: the reaction pressure is 0.2MPa, the reaction temperature is 100 ℃, and the liquid space velocity is 5.0h -1 Space velocity of hydrogen of 10h -1 . And (3) rectifying the refined trioxymethylene to further reduce the impurity content, thereby obtaining a rectified and refined product.
The composition and distribution of the main materials before and after refining are shown in Table 2.
TABLE 2 impurities content of crude trioxymethylene and after refining
| Impurity content (ppm) | MeOH | HCHO | H 2 O | HCOOH | CH 3 O(CH 2 O) 2 CH 3 |
| Crude trioxymethylene product | 50 | 440 | 660 | 350 | 360 |
| Catalytic refining of the product | 267 | 213 | |||
| Refining the product by rectification | 6 | 24 |
As can be seen from Table 2, the crude trioxymethylene also contains methanol, formaldehyde, water, formic acid and formaldehyde polymer, and the impurity content thereof reaches 1860ppm. The refined methanol-water mixed liquor only contains methanol and water impurities, the content of the impurities is reduced to be below 500ppm, and the content of the impurities can be reduced to be below 100ppm through rectification separation.
EXAMPLE 10 purification of commercially available trioxymethylene
The impurity levels of the commercially available trioxymethylene are shown in Table 3.
The refined catalyst 3 is loaded into a fixed bed refining reactor, and reduction pretreatment is carried out on the catalyst under the following reduction conditions: 250 ℃, 0.1Mpa and hydrogen space velocity of 100h -1 And the space velocity of nitrogen is 500h -1 。
Then refining the commercially available trioxymethylene by adopting a refining catalyst 6, wherein the process conditions are as follows: the reaction pressure is 0.5MPa, the reaction temperature is 80 ℃, and the liquid space velocity is 0.5h -1 Space velocity of hydrogen gas of 70h -1 . And (3) rectifying the refined trioxymethylene to further reduce the impurity content, thereby obtaining a rectified and refined product.
The composition and distribution of the main materials before and after refining are shown in Table 3.
TABLE 3 content of impurities in commercially available trioxymethylene and after refining
| Impurity content (ppm) | MeOH | HCHO | H 2 O | HCOOH |
| Commercially available trioxymethylene | 10 | 335 | 230 | 420 |
| Catalytic refining of the product | 30 | 17 |
As can be seen from Table 3, methanol, formaldehyde, water and formic acid were also contained in the commercially available trioxymethylene, and the impurity content thereof was 1035ppm. Only methanol and water impurities are contained after refining, and the impurity content is reduced to below 50 ppm.
EXAMPLE 11 purification of Synthesis product of Dioxypentacylic Compound
Weighing 500.0kg of 65% formaldehyde and 900.0Kg ethylene glycol were added to a 2.5L single neck round bottom flask, 120g of resin catalyst was added to the reactor at 105 deg.C, and the reactor outlet temperature was collected as 70-73 deg.C fractions to give the cyclization reaction product having the composition shown in Table 4 below. Putting the refined catalyst into a fixed bed refining reactor, and carrying out reduction pretreatment on the catalyst, wherein the reduction conditions are as follows: 230 ℃, 0.5Mpa and 120h of hydrogen space velocity -1 Space velocity of nitrogen 480h -1 。
Then refining the dioxolane reaction mixture by adopting a refining catalyst 6, wherein the process conditions are as follows: the reaction pressure is 1.5MPa, the reaction temperature is 100 ℃, and the liquid space velocity is 1.5h -1 Space velocity of hydrogen gas of 20h -1 . The composition and distribution of the main materials before and after refining are shown in Table 4.
TABLE 4 Dioxo pentacyclic reaction products
| Distribution (%) | MeOH | MF | DMM | DOL | HCHO | H 2 O | HCOOH | CH 3 O(CH 2 O) 2 CH 3 |
| Cyclization reaction product | 1.40 | 0.30 | 0.7 | 82.14 | 2.05 | 12.41 | 0.40 | 0.60 |
| Refining the product | 5.33 | 82.24 | 12.43 |
As can be seen from table 4, methyl Formate (MF), formaldehyde (HCHO) and formic acid (HCOOH) after refining are hydrofined to be methanol under the action of catalyst, and methylal and formaldehyde polymer are firstly depolymerized to be methanol and formaldehyde under the action of catalyst, and then are hydrofined to be methanol, so that the impurity composition of the dioxolane reactant is changed from 7 to 2.
EXAMPLE 12 purification of commercially available Dioxypentacycline
The impurity levels of the commercially available dioxolanes are shown in Table 5.
The refined catalyst 6 is loaded into a fixed bed refining reactor, and reduction pretreatment is carried out on the catalyst under the following reduction conditions: 250 ℃, 0.1Mpa and hydrogen space velocity of 100h -1 And the space velocity of nitrogen is 500h -1 。
Then refining the dioxolane with a refining catalyst 5 under the following process conditions: the reaction pressure is 0.4MPa, the reaction temperature is 90 ℃, and the liquid space velocity is 0.6h -1 Space velocity of hydrogen gas of 80h -1 . And (3) rectifying the refined dioxolane to further reduce the impurity content to obtain a rectified and refined product.
The composition and distribution of the main materials before and after refining are shown in Table 5.
TABLE 5 impurities content of commercially available Dioxopentacene and after purification
| Impurity content (ppm) | MeOH | HCHO | H 2 O | HCOOH |
| Commercially available trioxymethylene | 13 | 248 | 189 | 122 |
| Catalytic refining of the product | 20 | 29 |
As can be seen from Table 5, methanol, formaldehyde, water and formic acid were also present in the commercially available dioxolanes, and the impurity content reached 574ppm. Only methanol and water impurities are contained after refining, and the impurity content is reduced to below 50 ppm.
According to the refined catalyst prepared by the method, formaldehyde, formic acid, methyl formate, methylal and formaldehyde polymers in the crude reaction products obtained by synthesizing trioxymethylene and dioxolane are catalytically converted into methanol, so that the crude reaction products obtained by synthesizing trioxymethylene and dioxolane are converted into trioxymethylene, methanol and water systems or dioxolane, methanol and water systems which are easy to separate.
The method has the advantages of mild reaction process conditions in the refining process, simple flow, easy coupling with the subsequent separation process, great reduction of energy consumption in the production process and convenience for large-scale continuous production.
The method avoids the blockage of equipment such as pipelines, rectifying towers and the like in the subsequent separation process, reduces the corrosion problem of the equipment to the subsequent pipelines and equipment, and eliminates the appearance of multi-component azeotrope of the system.
The method realizes the purposes of aldehyde removal, deacidification and degreasing, has higher efficiency by adopting the original single multi-step refining process, reduces the energy consumption of the refining process and reduces the investment of a refining unit.
Compared with the traditional absorption, adsorption and extraction processes, no waste liquid and waste solid are generated in the catalytic refining process, and the refining process is environment-friendly; meanwhile, the formaldehyde, the formic acid and the methyl formate are converted into the methanol through catalytic refining and then used in the production process of the formaldehyde, so that the utilization rate of the raw materials is improved.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.
Claims (5)
1. A method for refining cyclic derivatives of formaldehyde, characterized in that it comprises the following steps: performing acid catalysis and hydrogenation catalysis refining on impurities in a trioxymethylene product or a dioxypentacyclic product by adopting a fixed bed reactor under the condition of a refining catalyst of a formaldehyde cyclic derivative so as to remove formaldehyde, formic acid and methyl formate contained in the trioxymethylene product or the dioxypentacyclic product;
the refined catalyst comprises an acidic active component and a hydrogenation active component; the acid active component is used for carrying out acid catalysis on impurities in a trioxymethylene product or a dioxypentacyclic product so as to decompose methylal or formaldehyde polymer into formaldehyde or methanol; the hydrogenation active component is used for carrying out catalytic hydrofining on impurities in a trioxymethylene product or a dioxolane product so as to catalytically convert formaldehyde, formic acid or methyl formate into methanol, the mass of the hydrogenation active component accounts for 10-70% of the total mass of the refined catalyst, the mass of the acidic active component accounts for 0.1-10% of the total mass of the refined catalyst, and the acidic active component is Al 2 O 3 SiO carrying an acidic substance 2 The hydrogenation active component comprises one or more components of a main catalyst component of Cu, ni and Pt, an auxiliary catalyst component of Zn, mg and Co, and a carrier of Al 2 O 3 、SiO 2 Activated carbon and molecular sieve.
2. The method according to claim 1, wherein the hydrogenation active component is a Cu-based catalyst system comprising a main catalyst component of Cu and a Co-catalyst component of Zn, mg or Co.
3. The method according to claim 1, wherein the hydrogenation-active component is a Pt-based catalyst system comprising Pt as a main catalyst component and Zn as a co-catalyst component.
4. The method for purifying cyclic derivatives of formaldehyde according to claim 1, wherein the acid catalyzesAnd the technological conditions of the hydrogenation catalytic refining are as follows: the reaction temperature is 80-120 ℃; the reaction pressure is 0.2-2Mpa; the liquid space velocity is 0.5-5h -1 The space velocity of hydrogen is 10-80h -1 。
5. The method for purifying cyclic derivatives of formaldehyde according to claim 1, wherein the process conditions of the acid-catalyzed and hydrocatalytic purification are as follows: the reaction temperature is 120 ℃; the reaction pressure is 2Mpa; the reaction space velocity is 1h -1 The space velocity of hydrogen is 50h -1 。
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