Catalyst for preparing 1, 4-butanediol through hydrogenation of succinate as well as preparation method and application of catalyst

Abstract

The invention provides a catalyst for preparing 1, 4-butanediol through hydrogenation of succinate and a preparation method and application of the catalyst, the structural formula of the catalyst is aAbBcCdD / (xZ1 + yZ2), a component A is selected from at least one of Ru, Os, Rh, Ir, Pd or Pt, a component B is selected from at least one of Cr, Mn, Fe, Co, Ni or Cu, a component C is an oxide of at least one metal of Ga, In, Ge, Sn, Pb, Sb, Bi, Se, Te, Nb, Mo, W, Re, Al, Ti, Zr or Zn, a component D is an oxide of at least one metal of alkaline earth or rare earth, and a component E is an oxide of at least one metal of alkaline earth or rare earth. Z1 is a carrier with high specific surface area, and Z2 is a carrier with high thermal conductivity; the mass percentage content of each component is as follows: a is 0.1 to 10 weight percent, b is 0 to 60 weight percent, c is 0 to 50 weight percent, d is 0 to 20 weight percent, x is 10 to 90 weight percent, and y is 0 to 40 weight percent; or a is equal to 0, b is equal to 15-70 wt%, c is equal to 0-80 wt%, d is equal to 0-15 wt%, x is equal to 0-45 wt%, y is equal to 0-20 wt%, and c and d are not equal to 0 at the same time. The catalyst has excellent catalytic performance on preparation of 1, 4-butanediol by hydrogenation of mono, di or polyester of succinic acid esters including monohydric, dihydric or polyhydric alcohols.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalyst preparation, and specifically, it is a catalyst for preparing 1,4-butanediol by hydrogenating succinic acid ester, its preparation method and application. Background Art

[0002] 1,4-butanediol is an important chemical intermediate and polyester monomer, and has wide applications in the fields of medicine, chemical industry, textile, papermaking, automobile and daily chemical industry, etc. 1,4-butanediol (BDO) can be used to produce polybutylene terephthalate (PBT) engineering plastics and fibers, polybutylene polyfatty acid ester (PBSX) biodegradable plastics, tetrahydrofuran (THF), polytetrahydrofuran ether (PTMEG) and polyurethane (PU), polar aprotic solvents γ-butyrolactone (GBL), pyrrolidone and N-methylpyrrolidone (NMP), coatings and plasticizers, etc.

[0003] At present, there are mainly three process routes for preparing BDO using maleic anhydride as a product or commodity raw material: direct hydrogenation of maleic anhydride, hydrolysis hydrogenation of maleic anhydride, and esterification hydrogenation of maleic anhydride. Among them, for the preparation of BDO by esterification hydrogenation of maleic anhydride, maleic anhydride first undergoes an esterification reaction with a lower monohydric alcohol (mostly C 1 ~C 4 alkanols) to form a maleic acid diester, and then the maleic acid diester undergoes multiple steps of hydrogenation to obtain BDO, while co-producing GBL and THF. CN110563933B and CN113512183A disclose a method for preparing BDO by two-step esterification and three-step hydrogenation of maleic anhydride: maleic anhydride is successively subjected to mono-esterification to form maleic acid mono-ester, double-esterification to form maleic acid diester, hydrogenation of maleic acid diester to form succinic acid diester, and two-step hydrogenation of succinic acid diester to obtain BDO with co-production of GBL and THF. CN112694602B reports a method for preparing BDO by three-step hydrogenation and one-step esterification of maleic anhydride, in which maleic anhydride is hydrogenated to form succinic anhydride, succinic anhydride is esterified with methanol to form dimethyl succinate (DMS), DMS is hydrogenated to form GBL, and GBL is hydrogenated to form BDO with co-production of THF. CN103946201B provides a method for producing BDO by two-stage tandem hydrogenation of dialkyl maleate in a mixed liquid / gas phase, and all use adiabatic fixed-bed reactors. In the first stage, Pd / C or Pd / Al 2 O 3 catalyst, at a feed liquid space velocity of 0.5~2.0 h -1 and a temperature of 80~130 °C, a hydrogen / ester molar ratio of 30~60 and a system pressure of 30~80 bar, dialkyl maleate is hydrogenated to form dialkyl succinate, the conversion rate of dimethyl maleate (DMM) is 100%, and the selectivity of DMS is~99%; in the second stage, a copper chromite or copper-zinc oxide catalyst containing 2~15 wt% BaO or MnO 2 is used, at a feed space velocity of 0.1~0.3 h-1 At a temperature of 160 - 190°C, a hydrogen / ester molar ratio of 30 - 60, and a pressure of 30 - 80 bar, dialkyl succinate is hydrogenated to produce BDO, and by-products GBL and THF. The conversion rate of DMS is 97.6 - 97.8%, the selectivity for BDO is 77.0 - 84.0%, for THF is 6.3 - 13.1%, and for GBL is 4.8 - 5.3%. The total selectivity of the three is 95.0 - 95.6%.

[0004] In summary, in the existing esterification and hydrogenation process starting from maleic anhydride via dialkyl maleate and dialkyl succinate, the reaction selectivity of BDO is relatively low, the total reaction yield does not exceed 81%, and a large amount of GBL and THF are produced as by-products, resulting in high consumption of maleic anhydride raw materials and high production costs for producing BDO. Obviously, the existing catalysts and their supporting processes limit the technological development of preparing BDO from maleic anhydride. Developing new routes and highly efficient catalysts has become the key to whether the maleic anhydride esterification hydrogenation process for producing BDO can be widely promoted and applied on a large scale.

[0005] Therefore, by introducing new materials (such as porous or mesoporous materials with high specific surface area, heat-conducting materials with excellent heat-transfer performance) as supports for supported metal catalysts, new routes (such as absorbing esterified gaseous crude maleic anhydride with BDO or esterifying maleic anhydride with BDO to obtain butylene glycol maleate, and then preparing BDO through two-step hydrogenation of butylene glycol succinate), and new processes (such as external circulation heat removal, efficient inter-stage heat exchange, or isothermal bed heat removal hydrogenation reaction technology), the purpose is to achieve highly dispersed metal active components, thereby improving catalyst activity and metal utilization rate, and timely withdrawing the reaction heat from the catalyst active sites to inhibit the formation of by-products and improve reaction selectivity. In addition, using the target product BDO as a maleic anhydride absorbent or esterifying agent and a hydrogenation reaction solvent can avoid introducing new impurities. At the same time, the large specific heat capacity Cp of BDO is used for heat storage, and efficient heat exchange or heat removal hydrogenation reaction process technology is used to timely and effectively withdraw the reaction heat to avoid excessive hot spot temperature or "temperature runaway" in the reactor bed layer, so as to achieve the purpose of improving the selectivity of the target product and the service life of the catalyst. In short, researching and developing maleic anhydride esterification hydrogenation catalysts with high activity, high selectivity, and mild reaction conditions, as well as new technical routes and new process technologies, are the main development directions for synthesizing BDO by the maleic anhydride method in the future. Summary of the Invention

[0006] In view of this, the present invention provides a catalyst for hydrogenating succinate to prepare 1,4-butanediol.

[0007] To achieve the above object, the technical solution of the present invention is specifically as follows:

[0008] A catalyst for hydrogenating succinate to prepare 1,4-butanediol, with the structural formula:

[0009] aAbBcCdD / (xZ1 + yZ2);

[0010] Wherein: Component A is selected from at least one of noble metals Ru, Os, Rh, Ir, Pd or Pt; Component B is selected from at least one of transition metals Cr, Mn, Fe, Co, Ni or Cu; Component C is selected from oxides of at least one metal among Ga, In, Ge, Sn, Pb, Sb, Bi, Se, Te, Nb, Mo, W, Re, Al, Ti, Zr or Zn; Component D is selected from oxides of at least one metal among alkaline earth or rare earth; Z1 is a high specific surface area support, selected from at least one of carbon materials, light magnesium oxide, alumina, silica, titanium oxide, zirconium oxide, zeolite molecular sieve, hydroxyapatite (HAP), diatomite, bentonite, kaolin or attapulgite; Z2 is a high thermal conductivity support, selected from at least one of graphite, graphene, α-Al 2 O 3 , Si, α-SiO 2 , BeO, SiC, Mo 2 C, BN or AlN; the mass percentage content of each component is: a = 0.1 - 10 wt%, b = 0 - 60 wt%, c = 0 - 50 wt%, d = 0 - 20 wt%, x = 10 - 90 wt%, y = 0 - 40 wt%; or, a = 0, b = 15 - 70 wt%, c = 0 - 80 wt%, d = 0 - 15 wt%, x = 0 - 45 wt%, y = 0 - 20 wt%, and c and d are not both 0 at the same time.

[0011] Furthermore, the catalyst is a single noble metal or double noble metal active component catalyst, or a double active component catalyst composed of a single noble metal and a single non-noble metal. Among them, A is selected from one or two of Ru, Os, Rh, Ir, Pd or Pt; B is selected from one of Cr, Mn, Fe, Co, Ni or Cu; C is selected from oxides of at least one metal among Ga, In, Ge, Sn, Pb, Sb, Bi, Se, Te, Nb, Mo, W, Re or Zn; D is selected from oxides of at least one metal among Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Nd, Sm, Er, Yb or Th; Z1 is selected from activated carbon (AC), mesoporous carbon (CMK), carbon nanotubes, light MgO, amorphous Al 2 O 3 , γ-Al 2 O 3 , θ-Al 2 O 3 , mesoporous Al 2 O 3 (MA), amorphous SiO 2 , silica gel, mesoporous SiO 2 (MS), amorphous TiO 2 , rutile, anatase, mesoporous TiO2 , ZrO 2 , mordenite (MOR), clinoptilolite (HEU), Y zeolite, beta zeolite, ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-41, MCM-48, MCM-49, MCM-50, MCM-56, SCM-14, SCM-15, AlPO 4 -11, SAPO-11, SAPO-34, ZRP-3, Silicalite-1, Silicalite-2, TS-1, TS-2, SBA-15, ZEO-2, ZEO-3, KIT-6, HAP, diatomite, bentonite, kaolin or attapulgite, and Z2 is selected from at least one of graphite, graphene, α-Al 2 O 3 , Si, α-SiO 2 , BeO, SiC or Mo 2 C; and the mass percentage content of each component is: a = 0.5 - 10 wt%, b = 0 - 15 wt%, c = 0 - 10 wt%, d = 0 - 10 wt%, x = 60 - 90 wt%, y = 0 - 35 wt%.

[0012] Furthermore, in the single noble metal or double noble metal active component catalyst, or the double active component catalyst composed of a single noble metal and a single non-noble metal, A is selected from one or two of Ru, Pd or Pt, B is selected from one of Mn, Fe, Ni or Cu, C is selected from oxides of one or two metals among Ga, In, Sn, Nb, Mo, W, Re or Zn, D is selected from oxides of one or two metals among Mg, Ba, La or Ce, Z1 is selected from AC, CMK, γ-Al 2 O 3 , θ-Al 2 O 3 , silica gel, MS, SiO 2 -Al 2 O 3 , TiO 2 , ZrO 2 , MCM-41, MCM-48, S-1, TS-1, SBA-15, HAP, diatomite or bentonite, and Z2 is selected from at least one of graphite, α-Al 2 O 3 , Si, α-SiO 2One or both of SiC, and the mass percentage content of each component is: a = 1.0 - 5.00%, b = 0 - 10.00%, c = 0 - 10.00%, d = 0 - 5.00%, x = 60 - 86%, y = 0 - 30%.

[0013] Further, in the single noble metal or double noble metal active component catalyst, or the double active component catalyst composed of a single noble metal and a single non-noble metal, the total mass ratio of the carrier x + y = 80 - 95%.

[0014] Further, in the single noble metal or double noble metal active component catalyst, or the double active component catalyst composed of a single noble metal and a single non-noble metal, the mass percentage content of each component is: a = 1.0 - 5.00%, b = 0 - 10.00%, c = 0 - 10.00%, d = 0 - 5.00%, x = 60.00 - 80%, y = 10 - 30%.

[0015] Further, the single noble metal or double noble metal active component catalyst, or the double active component catalyst composed of a single noble metal and a single non-noble metal is prepared by an impregnation method, including the following preparation steps:

[0016] S1. Ball-mill and sieve the powder of carrier Z1 or the mixed powder of carriers Z1 and Z2 to obtain a powder carrier.

[0017] S2. Impregnate the powder carrier prepared in step S1 with an aqueous solution of the precursor compound of component C, evaporate to dryness and crush under stirring, and calcine at 250 - 300 °C for 3 - 5 h in a nitrogen atmosphere to obtain a powder carrier loaded with the precursor of component C; impregnate the powder carrier loaded with the precursor of component C or the powder carrier prepared in step S1 with an aqueous solution of the precursor compound of component D or components B and D, cook at 60 - 85 °C for 0.5 - 1.0 h under stirring, then evaporate to dryness and crush, and calcine at 250 - 300 °C for 3 - 5 h in a nitrogen atmosphere to obtain a powder carrier loaded with the precursor of component D or C and D or B, C and D.

[0018] S3. Add a binder to the powder carrier prepared in step S1, or the powder carrier loaded with the precursor of component D or C and D or B, C and D prepared in step S2, and form it by rolling into balls, extrusion or tabletting, and calcine at 300 - 350 °C for 2 - 3 h and at 500 - 550 °C for 5 - 8 h in a nitrogen stream to obtain a granular carrier.

[0019] S4. Impregnate the powder support prepared in step S1 or the powder support loaded with component D or C and D or B, C and D precursors prepared in step S2 with an aqueous solution of component A precursor compound in equal volume and evaporate to dryness, or soak the granular support prepared in step S3 for 0.5 - 1.0 h and take it out for drying, then calcine it at 300 - 350 °C for 1 - 2 h and at 550 - 600 °C for 3 - 5 h in a nitrogen atmosphere to obtain a finished powder catalyst or a finished granular catalyst loaded with noble metals respectively.

[0020] Further, in step S1, the particle size of the powder support is ≤ 1.0 μm, preferably ≤ 0.5 μm.

[0021] Further, in step S3, the binder is selected from at least one of water, oxalic acid, tartaric acid, citric acid, shengfeng powder, stearic acid, glycerol, starch, polyethylene glycol (PEG), polypropylene oxide (PPG), polytetrahydrofuran (PTMG), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyvinylpyrrolidone (PVP), cellulose and methylcellulose, and the addition amount is 2.0 - 12.0 wt%; preferably, the binder is selected from at least one of water, shengfeng powder, glycerol, starch, PEG, PVA, PVP and methylcellulose, and the addition amount is 5.0 - 10.0 wt%.

[0022] The shape and size of the prepared granular catalyst are selected from spheres with a diameter of 1.0 - 5.0 mm, cylinders with a diameter of 1.0 - 5.0 mm and a length of 1 - 5 mm, clovers with a diameter of 1.0 - 5.0 mm and a length of 1 - 8 mm or strips with a diameter of 1.0 - 5.0 mm and a length of 1 - 8 mm, preferably spheres with a diameter of 1.6 - 3.0 mm, cylinders with a diameter of 1.6 - 3.0 mm and a length of 2 - 3 mm, clovers with a diameter of 1.6 - 3.0 mm and a length of 2 - 5 mm or strips with a diameter of 1.6 - 3.0 mm and a length of 2 - 5 mm.

[0023] Further, the catalyst is a single non-noble metal or double non-noble metal active component catalyst, wherein B is selected from one or two of Cr, Mn, Fe, Co, Ni or Cu, C is selected from at least one metal oxide of Ga, In, Mo, W, Re, Al, Ti, Zr or Zn, D is selected from at least one metal oxide of Mg, Ba, Sc, Y, La, Ce, Nd or Yb, and Z1 is selected from amorphous Al 2 O 3 、γ-Al 2 O 3 、θ-Al 2 O 3 、MA, amorphous SiO 2 、silica gel, MS, TiO 2 、ZrO 2, at least one of MCM-41, MCM-48, MCM-50, S-1, S-2, TS-1, TS-2, SBA-15, ZEO-2, ZEO-3, KIT-6, diatomite, bentonite, kaolin or palygorskite, and Z2 is selected from α-Al 2 O 3 , Si, α-SiO 2 , BeO, SiC or Mo 2 C; the mass percentage content of each component is: a = 0, b = 18-70%, c = 0-80%, d = 0-15%, x = 0-45%, y = 0-20%, and c and d are not both 0 at the same time.

[0024] Furthermore, in the single non-noble metal or double non-noble metal active component catalyst, B is selected from one or two of Cr, Mn, Fe, Co, Ni or Cu, C is selected from oxides of one or two metals of Ga, In, Mo, Al, Ti, Zr or Zn, D is selected from oxides of one or two metals of Mg, Ba, La or Ce, and Z1 is selected from γ-Al 2 O 3 , θ-Al 2 O 3 , MA, silica gel, MS, TiO 2 , ZrO 2 , MCM-41, MCM-48, S-1, TS-1, SBA-15, HAP, diatomite or bentonite, and Z2 is selected from α-Al 2 O 3 , Si, α-SiO 2 or at least one of SiC; the mass percentage content of each component is: a = 0, b = 40-70%, c = 0-50%, d = 0-10%, x = 0-40%, y = 0-15%, and c and d are not both 0 at the same time.

[0025] Furthermore, in the single non-noble metal or double non-noble metal active component catalyst, B is Cu or B is Cu and one of Cr, Mn, Fe, Co or Ni, and the mass percentage content of Cu is 40-55%.

[0026] Furthermore, in the single non-noble metal or double non-noble metal active component catalyst, the total mass ratio of the carrier x + y = 10-40%; preferably, the total mass ratio of the carrier x + y = 10-35%.

[0027] Further, in the single non-noble metal or double non-noble metal active component catalyst, when a = 0 and c = 0, b = 40 - 70%, d = 3.0 - 10.0%, x = 0 - 30%, y = 0 - 15%; or when a = 0 and d = 0, b = 40 - 70%, c = 18 - 45%, x = 0 - 30%, y = 0 - 15%.

[0028] Further, in the single non-noble metal or double non-noble metal active component catalyst, the mass percentage content of each component is: a = 0, b = 18 - 70%, c = 0 - 50%, d = 0 - 15%, x = 15 - 25%, y = 5 - 15%.

[0029] Further, the single non-noble metal or double non-noble metal active component catalyst is prepared by the co-precipitation method or the deposition-precipitation method, and the preparation steps are as follows:

[0030] L1. Ball-mill and sieve the powder of carrier Z1 or the powder of carrier Z2 or the mixed powder of Z1 and Z2 to obtain a powder carrier.

[0031] L2. Prepare aqueous solutions of precursor compounds of components B and D, an aqueous solution or an alcohol solution of a precursor compound of component C, and an aqueous sodium carbonate solution respectively. Under stirring, add these three solutions into a synthesis kettle simultaneously, or into a synthesis kettle pre-placed with the powder carrier prepared in step L1. Then, carry out steam cooking and aging at 75 - 85 °C for 1.0 - 3.0 h, and then filter, wash, dry, and crush the materials in sequence to obtain a catalyst precursor powder prepared by the co-precipitation method or the deposition-precipitation method.

[0032] L3. Calcinate the catalyst precursor powder prepared in step L2 in flowing air at 300 - 350 °C for 3 - 5 h and at 550 - 650 °C for 5 - 8 h to obtain a non-noble metal finished powder catalyst.

[0033] L4. Add a binder to the finished powder catalyst prepared in step L3, and form it by rolling into balls, extrusion, or tabletting. Then, calcinate it in flowing air at 300 - 350 °C for 2 - 3 h and at 500 - 600 °C for 3 - 5 h to obtain a non-noble metal finished particle catalyst.

[0034] Further, in step L1, the particle size of the powder carrier ≤ 1.0 μm, preferably ≤ 0.5 μm.

[0035] Further, in step L4, the binder is selected from at least one of water, oxalic acid, tartaric acid, citric acid, sesbania powder, stearic acid, glycerol, starch, polyethylene glycol (PEG), polyoxypropylene ether (PPG), polytetrahydrofuran (PTMG), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyvinylpyrrolidone (PVP), cellulose, and methylcellulose, and the addition amount is 2.0-12.0 wt%; preferably, the binder is selected from at least one of water, sesbania powder, glycerol, starch, PEG, PVA, PVP, and methylcellulose, and the addition amount is 5.0-10.0 wt%.

[0036] The shape and size of the prepared granular catalyst are selected from spheres with a diameter of 1.0-5.0 mm, cylinders with a diameter of 1.0-5.0 mm and a length of 1-5 mm, clovers with a diameter of 1.0-5.0 mm and a length of 1-8 mm, or strips with a diameter of 1.0-5.0 mm and a length of 1-8 mm. Preferably, the spheres have a diameter of 1.6-3.0 mm, the cylinders have a diameter of 1.6-3.0 mm and a length of 2-3 mm, the clovers have a diameter of 1.6-3.0 mm and a length of 2-5 mm, or the strips have a diameter of 1.6-3.0 mm and a length of 2-5 mm.

[0037] Further, the catalyst is a multi-component catalyst composed of noble metals and non-noble metals. Among them, A is selected from at least one of Ru, Os, Rh, Ir, Pd, or Pt, B is selected from at least one of Cr, Mn, Fe, Co, Ni, or Cu, C is selected from oxides of at least one metal among Mo, W, Re, Al, Ti, Zr, or Zn, D is selected from oxides of at least one metal among Mg, Ba, Sc, Y, La, Ce, Nd, or Yb, and Z1 is selected from AC, CMK, CNT, light MgO, amorphous Al 2 O 3 、γ-Al 2 O 3 、θ-Al 2 O 3 、MA, amorphous SiO 2 、silica gel, MS, TiO 2 、ZrO 2 、MOR, HEU, Y, β, ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-41, MCM-48, MCM-49, MCM-50, MCM-56, SCM-14, SCM-15, AlPO 4-11, at least one of SAPO-11, SAPO-34, ZRP-3, S-1, S-2, TS-1, TS-2, SBA-15, ZEO-2, ZEO-3, KIT-6, HAP, diatomite, bentonite, kaolin or attapulgite, and Z2 is selected from graphite, graphene, α-Al 2 O 3 , Si, α-SiO 2 , BeO, SiC, Mo 2 C, BN or AlN, and the mass percentage content of each component is: a = 0.1 - 5.0%, b = 30 - 60%, c = 0 - 50%, d = 0 - 20%, x = 0 - 40%, y = 0 - 15%, and c and d are not both 0 at the same time.

[0038] Furthermore, in the multi-active component catalyst composed of noble metal and non-noble metal, A is selected from at least one of Ru, Pd or Pt, B is selected from at least one of Mn, Fe, Co, Ni or Cu, C is selected from one or two of the oxides of Mo, Al, Ti, Zr or Zn, D is selected from one or two of the oxides of Mg, Ba, La or Ce, and Z1 is selected from AC, γ-Al 2 O 3 , silica gel, TiO 2 , ZrO 2 , ZSM-5, MCM-22, MCM-41, MCM-48, SCM-14, SAPO-34, ZRP-3, S-1, TS-1, SBA-15, HAP, diatomite or bentonite, and Z2 is selected from α-Al 2 O 3 , Si, α-SiO 2 , SiC or BN, and the mass percentage content of each component is: a = 0.5 - 3.00%, b = 35.00 - 55.00%, c = 0 - 45.00%, d = 0 - 15.00%, x = 0 - 30%, y = 0 - 10.00%, and c and d are not both 0 at the same time.

[0039] Furthermore, in the multi-active component catalyst composed of noble metal and non-noble metal, B is Cu or B is Cu and one of Cr, Mn, Fe, Co or Ni, and the mass percentage content of Cu is 35 - 50%.

[0040] Further preferably, in the multi-active component catalyst composed of noble metal and non-noble metal, the mass percentage content of each component is: a = 0.5 - 3.00%, b = 35.00 - 55.00%, c = 0, d = 10 - 15.00%, x = 0 - 30%, y = 0 - 10.00%; or, the mass percentage content of each component is: a = 0.5 - 3.00%, b = 35.00 - 55.00%, c = 10 - 45%, d = 0, x = 0 - 30%, y = 0 - 10.00%; or, the mass percentage content of each component is: a = 0.5 - 3.00%, b = 35.00 - 55.00%, c = 5 - 40%, d = 5.0 - 10.00, x = 0 - 30%, y = 0 - 10.00%.

[0041] Further, the catalyst is a multi-active component catalyst composed of noble metal and non-noble metal, and is prepared by an impregnation-coprecipitation combined method, including the following preparation steps:

[0042] Q1. Impregnate the Z1 powder carrier with an aqueous solution of the precursor compound of component C, evaporate to dryness and crush under stirring, calcine at 250 - 300 °C for 2 - 3 h and at 500 - 600 °C for 3 - 5 h in a nitrogen atmosphere to obtain a powder carrier loaded with the precursor of component C; then perform isovolumetric impregnation with an aqueous solution of the precursor compound of component A, evaporate to dryness, crush the cake, and calcine at 200 - 250 °C for 2 - 3 h and at 450 - 500 °C for 3 - 5 h in a nitrogen atmosphere to obtain a powder catalyst loaded with noble metal;

[0043] Q2. Prepare aqueous solutions of the precursor compounds of components B and D, an aqueous solution or alcohol solution of the precursor compound of component C, and an aqueous solution of sodium carbonate respectively. Stir and add these three solutions into the synthesis kettle at the same time, evaporate and cook at 75 - 85 °C for 1.0 - 3.0 h, then filter, wash, dry and crush the material, and calcine at 300 - 350 °C for 2 - 3 h and at 450 - 500 °C for 3 - 5 h in an air stream to obtain a non-noble metal powder catalyst prepared by the coprecipitation method;

[0044] Q3. Uniformly mix the powder catalyst loaded with noble metal prepared in step Q1, the non-noble metal powder catalyst prepared in step Q2 and the Z2 powder carrier, and calcine at 550 - 600 °C for 5 - 8 h in a nitrogen atmosphere to obtain a finished powder catalyst;

[0045] Q4. Add a binder to the finished powder catalyst prepared in step Q3, form it by rolling, extrusion or tabletting, and then calcine at 300 - 350 °C for 2 - 3 h and at 550 - 600 °C for 3 - 5 h in a nitrogen atmosphere to obtain a finished particle catalyst containing noble metal and non-noble metal double or multi-active components; or,

[0046] including the following preparation steps:

[0047] Q1 - Q4: The preparation steps are the same as L1 - L4;

[0048] Q5: Immerse the non - noble metal finished - product particles catalyst prepared in step L4 in an aqueous solution of the precursor compound of component A for 0.5 - 1.0 h. After taking it out and drying, calcine it at 200 - 250 °C for 2 - 3 h and at 450 - 500 °C for 3 - 5 h in a nitrogen atmosphere to obtain a finished - product particles catalyst containing noble and non - noble metal multi - active components.

[0049] Furthermore, the particle sizes of the Z1 powder carrier and the Z2 powder carrier are ≤1.0 μm, preferably ≤0.5 μm.

[0050] Furthermore, in step Q4, the binder is selected from at least one of water, oxalic acid, tartaric acid, citric acid, sesbania powder, stearic acid, glycerol, starch, polyethylene glycol (PEG), polyoxypropylene ether (PPG), polytetrahydrofuran (PTMG), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyvinylpyrrolidone (PVP), cellulose, and methylcellulose, and the addition amount is 2.0 - 12.0 wt%; preferably, the binder is selected from at least one of water, sesbania powder, glycerol, starch, PEG, PVA, PVP, and methylcellulose, and the addition amount is 5.0 - 10.0 wt%;

[0051] The shapes and sizes of the prepared particle catalysts are selected from spheres with a diameter of 1.0 - 5.0 mm, cylinders with a diameter of 1.0 - 5.0 mm and a length of 1 - 5 mm, clovers with a diameter of 1.0 - 5.0 mm and a length of 1 - 8 mm, or strips with a diameter of 1.0 - 5.0 mm and a length of 1 - 8 mm. Preferably, they are spheres with a diameter of 1.6 - 3.0 mm, cylinders with a diameter of 1.6 - 3.0 mm and a length of 2 - 3 mm, clovers with a diameter of 1.6 - 3.0 mm and a length of 2 - 5 mm, or strips with a diameter of 1.6 - 3.0 mm and a length of 2 - 5 mm.

[0052] Furthermore, to prepare a catalyst with the structural formula aAbBcCdD / (xZ1 + yZ2), the precursor compound of component A is selected from ruthenium chloride, ruthenium acetate, ammonium chlororuthenate, osmium chloride, rhodium chloride, rhodium iodide, rhodium acetate, iridium chloride, chloroiridic acid, palladium chloride, palladium nitrate, palladium acetate, ammonium chloropalladate, palladium acetylacetonate, palladium ammonia complex salt, or Schiff - base palladium complex, chloroplatinic acid, ammonium chloroplatinate, preferably at least one of ruthenium trichloride, osmium trichloride, rhodium trichloride, chloroiridic acid, palladium dichloride, or chloroplatinic acid;

[0053] The precursor compound of component B is selected from at least one of chlorides, nitrates, acetates, or oxalates of Cr, Mn, Fe, Co, Ni, or Cu; preferably, the precursor compound of component B is selected from at least one of chromium nitrate, manganese acetate, iron nitrate, cobalt nitrate, nickel nitrate, or copper nitrate;

[0054] The precursor compound of component C is selected from at least one of chlorides, nitrates, acetates, oxalates, ammonium salts or oxides of Ga, In, Ge, Sn, Pb, Sb, Bi, Se, Te, Nb, Mo, W, Re, Al, Ti, Zr or Zn; preferably, the precursor compound of component C is selected from at least one of gallium nitrate, indium nitrate, germanium tetrachloride, tin dichloride, lead acetate, antimony trichloride, bismuth nitrate, selenium dioxide, tellurium dioxide, niobium oxalate, ammonium paramolybdate, ammonium tungstate, rhenium heptoxide, aluminum nitrate, tetrabutyl titanate, zirconium nitrate or zinc acetate;

[0055] The precursor compound of component D is selected from at least one of chlorides or nitrates of alkaline earth or rare earth elements, preferably, the precursor compound of component D is selected from at least one of nitrates of alkaline earth or rare earth elements.

[0056] The present invention also provides an application of the above-mentioned catalyst, and the catalyst is used for the reaction of hydrogenating succinate to prepare 1,4-butanediol. The process of the hydrogenation reaction is as follows: Feed the succinate solution with a preheated temperature of 120-180 °C and a concentration of 10-100 wt% into a slurry bed or a fixed bed reactor filled with the catalyst pre-reduced and activated in advance for catalytic hydrogenation reaction to obtain 1,4-butanediol product;

[0057] The process conditions of the hydrogenation reaction are: the weight hourly space velocity of the succinate solution feed is 0.05-2.00 h -1 , the reaction temperature is 140-300 °C, the hydrogen pressure is 1.5-10.0 MPa, and the hydrogen-to-ester molar ratio is 20-200; preferably, the weight hourly space velocity of the feed is 0.10-1.50 h -1 , the reaction temperature is 150-280 °C, the hydrogen pressure is 2.0-8.0 MPa, and the hydrogen-to-ester molar ratio is 35-150; more preferably, the weight hourly space velocity of the feed is 0.20-1.00 h -1 , the reaction temperature is 150-250 °C, the hydrogen pressure is 2.5-6.5 MPa, and the hydrogen-to-ester molar ratio is 50-100.

[0058] Furthermore, before the hydrogenation reaction, the catalyst is reduced and activated. When a slurry bed reactor is used for the hydrogenation reaction, an out-of-reactor pressure reduction and activation method is adopted; when a fixed bed reactor is used for the hydrogenation reaction, an in-situ online reduction and activation method is adopted. The process conditions of the reduction and activation are: the reduction temperature is 150-450 °C, the hydrogen volumetric hourly space velocity is 10-200 h -1 , the hydrogen pressure is 0.1-5.0 MPa; preferably, the reduction temperature is 180-430 °C, the hydrogen volumetric hourly space velocity is 30-150 h -1, the hydrogen pressure is 0.5 to 2.5 MPa; more preferably, the reduction temperature is 210 to 410 °C, and the hydrogen volumetric space velocity is 50 to 100 h -1 , the hydrogen pressure is 1.0 to 2.0 MPa.

[0059] Further, the slurry bed reactor is a jacket heat exchange or external circulation heat removal fully mixed slurry bed reactor, and the fixed bed reactor is an inter-stage heat exchange adiabatic fixed bed reactor or a shell and tube isothermal fixed bed reactor.

[0060] Further, the raw material succinate solution is a pure liquid succinate, or a lower monohydric alcohol solution corresponding to the succinate, or a 1,4-butanediol, γ-butyrolactone or tetrahydrofuran solution of the succinate.

[0061] Further, the concentration of the raw material succinate solution is 15% to 100%, such as 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%.

[0062] Further, the succinate includes a monoesters or / and diesters of succinic acid with monohydric alcohols, or monoesters, diesters, triesters or / and di- or poly-succinates of succinic acid with dihydric or polyhydric alcohols; wherein:

[0063] The monohydric alcohol includes C 1 ~C 20 fatty alcohols, C 7 ~C 16 aromatic alcohols, C 3 ~C 16 heterocyclic alcohols or their substituted alcohols; preferably methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, neopentanol, isooctanol, allyl alcohol, butenol, isopentenol, propargyl alcohol, butynol, cyclopentanol, cyclohexanol, 4-methylcyclohexanol, cyclohexylmethanol, cyclohexylethanol, cyclohexylpropanol, benzyl alcohol, α-phenylethanol, β-phenylethanol, α-methylphenylethanol, hydrocinnamyl alcohol, cinnamyl alcohol, glycidol, furfuryl alcohol, tetrahydrofurfuryl alcohol, nicotinyl alcohol, 2-pyridinemethanol, 4-piperidinemethanol, 2-thiophenemethanol, 2-chloroethanol, 3-chloropropanol, 4-chlorobutanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol; more preferably methanol, ethanol, butanol or isooctanol;

[0064] The dihydric or polyhydric alcohol includes C 2 ~C 10 fatty dihydric or polyhydric alcohols, C 8 ~C 16 aromatic dihydric alcohols, C 5 ~C 10Heterocyclic diols or their substituted alcohols; preferably ethylene glycol, diethylene glycol, triethylene glycol, oligomeric ethylene glycol (PEG), 1,2-propanediol, dipropylene glycol, oligomeric propylene glycol (PPG), 1,3-propanediol, 1,4-butanediol, oligomeric tetramethylene ether glycol (PTMEG), 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol (glycerin), trimethylolethane, trimethylolpropane, pentaerythritol, erythritol, xylitol, mannitol, sorbitol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, o-phthalyl alcohol, m-phthalyl alcohol, p-phthalyl alcohol, 1,4-naphthalenedimethanol, 1,8-naphthalenedimethanol, 2,2'-biphenyldimethanol, 4,4'-biphenyldimethanol, 2,5-furandimethanol, 2,6-pyridinedimethanol; more preferably 1,4-butanediol, 1,4-butenediol or 1,4-butynediol.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] (1) The present invention for the first time adopts a new technical route for the hydrogenation of butylene succinate, which lays a foundation for the preparation of 1,4-butanediol (BDO) through a two-step hydrogenation process of butylene succinate, especially for the maleic acid butanediol ester prepared by ring-opening esterification of maleic anhydride with BDO as the starting material, especially the maleic acid butanediol ester obtained by absorbing and esterifying the gaseous crude maleic anhydride in an industrial maleic anhydride plant with BDO as both the absorbent and esterifying agent. By using the novel and efficient catalyst provided by the present invention and supporting new processes and technical routes, the production of BDO from maleic anhydride can not only significantly shorten the process flow, reduce the device investment, and simplify the operation process, but also significantly reduce the raw material and energy consumption.

[0067] (2) By introducing a high-thermal-conductivity carrier into the noble metal catalyst supported on a porous carrier with low metal content, the present invention improves the thermal conductivity of the catalyst, can timely withdraw the reaction heat from the active sites of the catalyst, avoid the accumulation of reaction heat at the active centers, and thus inhibit the occurrence of side reactions and improve the selectivity of the target reaction.

[0068] (3) By introducing a porous or mesoporous carrier, or a composite carrier composed of a porous or mesoporous material and a thermal-conductivity material, into the transition metal bulk catalyst with high metal content, the present invention increases the specific surface area of the catalyst, enables the highly dispersed metal active components, inhibits the agglomeration and growth of the active metal, and thus improves the catalytic activity and metal utilization rate.

[0069] (4) The catalyst of the present invention is prepared by a method combining impregnation - coprecipitation - mixing or deposition precipitation - impregnation, and contains both noble metal and non - noble metal active components, dual promoters (a refractory high - valence metal oxide structural promoter and a basic oxide electronic promoter), and dual supports (a porous or mesoporous material and a high - thermal - conductivity material support). It not only combines the characteristics of a single - loaded noble metal catalyst and a bulk non - noble metal catalyst but also has excellent heat - conduction and heat - transfer performance, showing high activity and high selectivity for the hydrogenation of succinic acid esters to prepare BDO. The conversion rate of succinic acid esters is 98.6 - 99.8%, and the selectivity for BDO is 93.5 - 96.1%.

[0070] (5) The present invention adopts a slurry - bed hydrogenation reaction process with external - circulation cooling heat exchange, an adiabatic fixed - bed with inter - stage quenching heat exchange, or an isothermal fixed - bed with shell - and - tube medium heat removal, which can avoid excessive hot - spot temperature or temperature runaway in the reactor bed, thereby improving the selectivity and yield of the target product, preventing sintering of the metal active components, and prolonging the service life of the catalyst. In addition, the present invention uses the target product BDO or an alkanol corresponding to the raw material succinic acid ester (a hydrogenation co - product) or the by - product THF as the hydrogenation reaction solvent, which can avoid the introduction of new impurities from outside the system. Especially when using BDO with a higher boiling point, a larger specific heat capacity, and a larger latent heat of vaporization as the solvent, it can effectively store heat and avoid temperature runaway. Detailed implementation manners

[0071] The following further elaborates the present invention in combination with specific embodiments. It should be noted that the embodiments described in this part are only a part of the embodiments of the present invention, not all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0072] Symbol description: MBS is monobutyl succinate - monobutylene glycol ester, DBS is dibutyl succinate - dibutylene glycol ester, BDS is dibutyl succinate - monobutylene glycol diester, PBS is polybutylene glycol succinate, CBS is mixed butylene glycol succinate; MMS is monomethyl succinate, DMS is dimethyl succinate, MES is monoethyl succinate, DES is diethyl succinate, MDS is monobutyl succinate, DDS is dibutyl succinate, MOS is monoisooctyl succinate, DOS is diisooctyl succinate, DAS is diallyl succinate, DCS is dicyclohexyl succinate, MPS is monobenzyl succinate, MTS is monotetrahydrofurfuryl succinate, DXS is dibutylene glycol succinate - dibutene glycol diester, MQS is monobutynediol succinate - monobutynediol monoester; BDO is 1,4 - butanediol, WXC is semi - hydrogenated product 4 - hydroxybutyric acid - butylene glycol mono - or diester, GBL is γ - butyrolactone, THF is tetrahydrofuran.

[0073] Examples 1 - 13

[0074] Noble metal active component or noble metal and non-noble metal dual active component catalyst, its preparation method and application

[0075] Ⅰ. Preparation of catalyst:

[0076] Prepare the catalyst according to the catalyst composition and the mass percentage content of each component shown in Table 1. The preparation process is as follows:

[0077] S1. Mix the high specific surface porous or mesoporous material Z1 support mesoporous carbon (CMK), γ-Al 2 O 3 , amorphous SiO 2 , mesoporous molecular sieve SBA-15 or / and TiO 2 (anatase) powder, or mix the Z1 support with the high thermal conductivity material Z2 support graphite, corundum (α-Al 2 O 3 ), silicon powder (Si) or silicon carbide (SiC) powder, ball mill and sieve to obtain a powder support TiO 2 , SBA-15, CMK-graphite, γ-Al 2 O 3 -α-Al 2 O 3 , γ-Al 2 O 3 -Si, TiO 2 -Si, SiO 2 -Si, SiO 2 -SiC or SiO 2 -TiO 2 -Si;

[0078] S2. Immerse the powder support obtained in step S1 with an aqueous solution of component C compounds rhenium heptoxide, stannous chloride, niobium oxalate, ammonium tungstate or ammonium paramolybdate, evaporate to dryness and crush under stirring, and calcine at 300 °C for 3 h in a nitrogen stream to obtain a powder support ReO x / SBA-15, ReO x / CMK-graphite, SnO 2 / γ-Al 2 O 3 -α-Al 2 O 3 , SnO 2 / SiO 2 -Si, Nb 2 O 5 / SiO 2 -SiC, WO 3 / TiO 2 -Si, WO 3 / TiO2 , WO 3 / γ-Al 2 O 3 -Si or MoO 3 / SiO 2 -TiO 2 -Si;

[0079] The powder carrier SiO 2 -TiO 2 -Si or the powder carrier WO loaded with the precursor of component C 3 / γ-Al 2 O 3 -Si, MoO 3 / SiO 2 -TiO 2 -Si, ReO x / SBA-15, ReO x / CMK-graphite or Nb 2 O 5 / SiO 2 -SiC, cooked at 80 °C for 45 min under stirring, evaporated to dryness, crushed, and then calcined at 300 °C for 3 h in a nitrogen atmosphere to obtain the powder carrier BaO / SiO loaded with the precursor of component D or components B and C or components C and D 2 -TiO 2 -Si, CuO-WO 3 / γ-Al 2 O 3 -Si, CoO-MoO 3 / SiO 2 -TiO 2 -Si, ReO x -CeO 2 / SBA-15, ReO x -CeO 2 / CMK-graphite or Nb 2 O 5 -CeO 2 / SiO 2 -SiC;

[0080] S3. Add 5 wt% methyl cellulose as the binder and 5 wt% water to the powder carrier loaded with the precursor of component C or D or B and C or C and D prepared in step S2, extrude and form into clover-shaped particles with a diameter of 2.2 mm and a length of 3.0 - 5.0 mm, and then calcine at 350 °C for 3 h and 550 °C for 5 h in a nitrogen stream to obtain the supported particle carrier SnO 2 / γ-Al 2 O 3-α-Al 2 O 3 、SnO 2 / SiO 2 -Si、WO 3 / TiO 2 -Si、WO 3 / TiO 2 、BaO / SiO 2 -TiO 2 -Si、Cu-WO 3 / γ-Al 2 O 3 -Si、CoO-MoO 3 / SiO 2 -TiO 2 -Si、ReO x -CeO 2 / SBA-15 or Nb 2 O 5 -CeO 2 / SiO 2 -SiC;

[0081] S4. Impregnate the powder carrier SiO 2 -TiO 2 -Si or the powder carrier WO loaded with component C or the precursors of C and D obtained in step S2 3 / TiO 2 、ReO x -CeO 2 / CMK-graphite or ReO x -CeO 2 / SBA-15 and evaporate to dryness, or soak the supported particle carrier SnO obtained in step S3 2 / γ-Al 2 O 3 -α-Al 2 O 3 、SnO 2 / SiO 2 -Si、WO 3 / TiO 2 -Si、WO 3 / TiO 2 、BaO / SiO 2 -TiO 2 -Si、CuO-WO 3 / γ-Al 2 O 3 -Si、CoO-MoO 3 / SiO 2 -TiO2 -Si, ReO x -CeO 2 / SBA - 15 or Nb 2 O 5 -CeO 2 / SiO 2 -SiC for 45 min and taken out for drying, then calcined at 350 °C for 2 h and 600 °C for 5 h in a nitrogen atmosphere to obtain Pt - WO 3 / TiO 2 、Ru / SiO 2 -TiO 2 -Si, Pt - ReO z -CeO 2 / CMK - graphite or Pt - ReO x -CeO 2 / SBA - 15 finished powder catalyst and Ru - SnO 2 / γ - Al 2 O 3 -α - Al 2 O 3 、Ru - BaO / SiO 2 -TiO 2 -Si, Pt - ReO x -CeO 2 / CMK - graphite, Pt - Ru - SnO 2 / SiO 2 -Si, Pt - WO 3 / TiO 2 -Si, Pt - WO 3 / TiO 2 、Pd - Nb 2 O 5 -CeO 2 / SiO 2 -SiC, Ru - CuO - WO 3 / γ - Al 2 O 3 -Si or Pt - CoO - MoO 3 / SiO 2 -TiO 2 -Si finished particle catalyst, and marked as Cat - 1 to Cat - 13 accordingly. The specific composition and morphology of the catalyst are shown in Table 1. For example, for catalyst number Cat - 1, its composition is: 1.0Pt - 9.0WO 3 / 80.0TiO 2 , which means that in the catalyst composition, the mass percentage of the noble metal Pt is 1.0%, and the mass percentage of WO 3 is 9.0%, and the carrier TiO 2The mass percentage is 80%.

[0082] Appendix 1 Catalyst Composition, Morphology and Corresponding Numbers for the Hydrogenation of Succinate to 1,4-Butanediol

[0083]

[0084]

[0085] Ⅱ. Reduction Activation of the Catalyst

[0086] Before using the catalyst for catalytic hydrogenation reaction, load the above-prepared finished powder catalyst into a tubular furnace and introduce hydrogen for reduction activation; or load the finished particle catalyst into a fixed-bed reactor (inter-stage quenching heat exchange adiabatic fixed-bed reactor or shell-and-tube isothermal fixed-bed reactor) and introduce hydrogen for in-situ reduction activation. Reduction conditions: temperature 250 °C, hydrogen volume space velocity 50 h -1 , hydrogen pressure 1.0 MPa, and reduce until no more water is generated, then the reduction activation of the catalyst is completed.

[0087] Ⅲ. Catalytic Hydrogenation Reaction

[0088] Transfer the reduced and activated powder catalyst to an external circulation heat exchange full-mixed slurry bed reactor, or adjust the operating parameters of the fixed-bed reactor filled with the in-situ reduced and activated particle catalyst, and introduce the raw materials and hydrogen according to the raw materials (BDO solution of butylene succinate) and concentrations, and reaction operating conditions shown in Appendix 2 to carry out the reaction for the hydrogenation of butylene succinate to 1,4-butanediol. The hydrogenation catalysts, reaction conditions and reaction results used in each specific example are listed in Table 2.

[0089] Table 2 Hydrogenation Catalysts, Reactor Forms, Reaction Process Conditions and Results Corresponding to Examples 1-13

[0090]

[0091]

[0092] According to the results in Table 2, it can be seen that when using the catalysts Cat-1 to 13 prepared above for the hydrogenation reaction of butylene succinate to 1,4-butanediol, at a BDO solution concentration of 15-60 wt% of butylene succinate and a feed space velocity of 0.20-0.50 h -1, under the operating conditions of a hydrogen / (ester group and carboxyl group) molar ratio of 75 to 120, a reaction temperature of 150 to 250 °C, and a system pressure of 3.0 to 8.0 MPa, the conversion rate of butylene succinate is 89.5 to 100%, the selectivity for 1,4-butanediol (BDO) is 85.5 to 95.5%, the semi-hydrogenated product 4-hydroxybutyric acid butylene mono- or diester (WXC) is 0.6 to 5.1%, γ-butyrolactone (GBL) is 0.8 to 4.3%, and tetrahydrofuran (THF) is 0.6 to 10.5%. It shows that the noble metal catalyst has good performance in the hydrogenation reaction of butylene succinate.

[0093] In addition, by comparing the catalyst compositions and reaction results of Examples 9 and 10, it can be found that under the same reaction process conditions, the catalyst 1.0Pt-9.0WO of Example 10 without the heat-conducting carrier Z2 3 / 80.0TiO 2 , for the hydrogenation reaction of BDS, its conversion rate is 99.9%, the selectivity for BDO is 93.8%, the selectivity for WXC is 2.1%, the selectivity for GBL is 1.2%, and the selectivity for THF is 2.8%. Compared with the catalyst 1.0Pt-9.0WO of Example 9 with the heat-conducting carrier Z2 3 / 70.0TiO 2 -10.0Si, the selectivity for the target product BDO is lower, and the selectivity for the by-product THF increases significantly. Obviously, introducing an appropriate amount of heat-conducting carrier into the noble metal catalyst with a high-surface carrier is beneficial to improving the selectivity for the target product BDO.

[0094] Examples 14 to 25

[0095] Non-noble metal active component catalyst and its preparation method and application

[0096] Ⅰ. Preparation of catalyst:

[0097] According to the catalyst composition shown in Table 3, based on the content by mass of the oxides of components B, C, and D elements, measure, and the preparation process of the catalyst is as follows:

[0098] L1. Use the high specific surface porous or mesoporous material Z1 carrier mesoporous SiO 2 (MS), mesoporous molecular sieve SBA-15 or silica gel powder, or the high heat-conducting material Z2 carrier silicon powder (Si) or SiC, or the mixed powder of the Z1 carrier MS or silica gel and the Z2 carrier Si, ball mill and screen to obtain a powder carrier MS, SBA-15, SiO 2 , Si, SiC, MS-Si or SiO 2 -Si with a particle size of 100 to 250 nm.

[0099] L2. Prepare aqueous solutions of component B compounds chromium nitrate, manganese acetate, iron nitrate, nickel nitrate, and / or copper nitrate, and component D compounds magnesium nitrate, barium nitrate, or cerium nitrate respectively. Also prepare an aqueous solution or an alcohol solution of component C compounds indium nitrate, ammonium heptamolybdate, aluminum nitrate, tetrabutyl titanate, zirconium nitrate, and / or zinc acetate, and an aqueous solution of sodium carbonate. While stirring, add these three solutions simultaneously into a synthesis kettle, or into a synthesis kettle that has been pre-loaded with the powder carriers MS, SBA-15, SiO 2 , Si, SiC, MS-Si, or SiO 2 -Si prepared in step L1. Then, cook and age at 80 °C for 2.0 h, and then filter, wash, dry, and crush the materials in sequence to obtain the precursor powders of the catalysts NiInAlBaO, CuZnZrCeO, CuZnMnAlO, CuCrBaO / MS-Si, CuFeMgO / SBA-15, CuNiCeO / MS, CuZnCeO / SiO 2 , CuZnMnO / SiO 2 -Si, CuZnAlBaO / SiC, or CuZnTiO / Si prepared by the co-precipitation method or the deposition-precipitation method.

[0100] L3. Calcinate the catalyst precursor powders from step L2 in an air stream at 350 °C for 3 h and at 600 °C for 6 h to obtain the finished powder catalysts NiInAlBaO, CuFeMgO / SBA-15, CuNiCeO / MS, or CuZnTiO / Si, and label them as Cat-14 to Cat-17 respectively. The specific composition and morphology of the catalysts are shown in Table 3. For example, for catalyst number Cat-14, its composition is: 18.0Ni3.5In75.0Al3.5BaO, which means that in its catalyst composition, the content of NiO is 18.0 wt%, In 2 O 3 content is 3.5 wt%, Al 2 O 3 content is 75.0 wt% and Ba content is 3.5 wt%.

[0101] L4. Add 8 wt% methyl cellulose and 5 wt% water as binders to the finished powder catalysts from step L3, and form them into cylindrical particles with a diameter of 2.0 mm and a height of 2.0 mm by tabletting. Then, calcinate in an air stream at 350 °C for 3 h and at 600 °C for 5 h to obtain the finished particle catalysts CuCrBaO / MS-Si, CuNiCeO / MS, CuZnCeO / SiO 2 , CuZnMnO / SiO 2-Si, CuZnAlBaO / SiC, CuZnZrCeO, CuZnTiO / Si or CuZnMnAlO, and are correspondingly labeled as Cat-18 to Cat-25. The specific composition and morphology of the catalysts are shown in Table 3. For example, for catalyst number Cat-18, its composition is: 40.0Cu25.0Cr5.0BaO / 25.0MS-5.0Si, which means that in its catalyst composition, the content of CuO is 40.0wt%, Cr 2 O 3 content is 25.0wt%, Ba content is 5.0wt%, MS content is 25.0wt% and silicon powder content is 5.0wt%.

[0102] Table 3 Composition, morphology and corresponding numbers of the catalysts prepared in Examples 14 to 25

[0103]

[0104] II. Reduction activation of the catalyst: Load the finished powder catalyst into a tubular furnace and introduce hydrogen for reduction activation; or load the finished granular catalyst into a fixed bed reactor (inter-stage quenching heat exchange adiabatic fixed bed reactor or shell-and-tube isothermal fixed bed reactor) and introduce hydrogen for in-situ reduction activation. Reduction conditions: temperature 380°C, hydrogen volume space velocity 100h -1 , hydrogen pressure 2.0MPa, and reduce until no more water is generated.

[0105] III. Catalytic hydrogenation reaction: Transfer the reduced and activated powder catalyst to an external circulation heat exchange full-mixed slurry bed reactor, or adjust the operating parameters of the fixed bed reactor filled with the in-situ reduced and activated granular catalyst, and introduce the raw materials and hydrogen according to the raw materials (BDO solution of butylene succinate) and concentrations, and reaction operating conditions shown in Appendix 4 to carry out the corresponding reaction of hydrogenating butylene succinate to prepare 1,4-butanediol. The hydrogenation catalysts, reaction conditions and reaction results used in each specific example are listed in Table 4.

[0106] Table 4 Hydrogenation catalysts, reactor forms, reaction process conditions and results corresponding to Examples 14 to 25

[0107]

[0108] From the results in Table 4, it can be seen that using a non-noble metal active component catalyst, at a BDO solution concentration of butylene succinate of 10 - 50wt% and a feed space velocity of 0.20 - 1.00h -1Under the operating conditions of a hydrogen / (ester group and carboxyl group) molar ratio of 50 to 100, a reaction temperature of 180 to 260 °C, and a system pressure of 2.5 to 8.0 MPa, the conversion rate of butylene succinate is 97.6 to 99.8%, and the selectivities are 83.6 to 96.5% for 1,4-butanediol (BDO), 0.3 to 5.1% for WXC, 0.5 to 4.2% for GBL, and 1.3 to 6.2% for THF. It shows that the non-noble metal catalyst described in the present invention also has good catalytic performance for the hydrogenation of butylene succinate.

[0109] Comparative Example 1

[0110] Hydrogenation performance of butylene succinate over non-noble metal catalyst without high specific surface area support

[0111] Ⅰ. Preparation of catalyst:

[0112] The preparation process of the catalyst in this comparative example is different from that in Example 15 in that the catalyst is prepared by the co-precipitation method, and the high specific surface area mesoporous support SBA-15 is not added during the preparation process. The mass composition of this catalyst CuFeMgO is CuO:Fe 2 O 3 :MgO = 50.0:10.5:4.5.

[0113] Ⅱ. Reduction activation of catalyst: The same as in Example 15.

[0114] Ⅲ. Catalytic hydrogenation reaction: The same as in Example 15, applied to the hydrogenation of MBS to 1,4-butanediol.

[0115] The results of the MBS hydrogenation reaction are as follows: the conversion rate of MBS is 86.3%, the selectivity of BDO is 91.3%, the selectivity of WXC is 2.3%, the selectivity of GBL is 2.5%, and the selectivity of THF is 3.1%. Compared with the results of Example 15, it can be seen that the conversion rate of MBS and the selectivity of the product BDO are significantly reduced, and the semi-hydrogenation products WXC and GBL are significantly increased. Obviously, compared with the catalyst prepared by the deposition-precipitation method with a high specific surface area support, the non-noble metal catalyst prepared by the co-precipitation method has lower catalytic activity under the same reaction process conditions, manifested as a low conversion rate and the formation of more semi-hydrogenation products and GBL.

[0116] Examples 26 - 37

[0117] Noble metal and non-noble metal dual or multi-active component catalyst and its preparation by impregnation-co-precipitation-mixing method and application to the hydrogenation reaction of butylene succinate

[0118] Ⅰ. Preparation of catalyst:

[0119] Weigh according to the catalyst composition and the mass percentage content of each component shown in Appendix 5. The catalyst preparation process is as follows:

[0120] Q1. Use the compound Re of component C 2 O 7 or SnCl 2 aqueous solution to impregnate the Z1 powder carriers γ-Al 2 O 3 with particle sizes of 100 - 250 nm, CMK or SBA-15. Stir and evaporate to dryness and then crush. Calcinate at 300 °C for 2 h and 600 °C for 5 h in a nitrogen atmosphere to obtain the powder carriers SnO 2 / γ-Al 2 O 3 、ReO x / CMK or ReO x / SBA-15 loaded with the precursor of component C; then use the aqueous solution of ruthenium trichloride or chloroplatinic acid, the compound of component A, for equal-volume impregnation. After evaporation to dryness, crush the material cake and calcinate at 250 °C for 2 h and 500 °C for 5 h in a nitrogen atmosphere to obtain the powder catalyst loaded with noble metals Pt-SnO 2 / γ-Al 2 O 3 、Pt-ReO x / CMK or Ru-ReO x / SBA-15.

[0121] Q2. Prepare aqueous solutions of the compounds of component B, manganese acetate, nickel nitrate or / and copper nitrate, and the compounds of component D, barium nitrate or cerium nitrate, respectively, aqueous solutions or alcohol solutions of the compounds of component C, aluminum nitrate, tetrabutyl titanate, zirconium nitrate or / and zinc acetate, and an aqueous solution of sodium carbonate. Stir and add these three solutions into the synthesis kettle simultaneously. Cook and age at 80 °C for 2.0 h, then filter, wash, dry and crush the material, and calcinate at 350 °C for 3 h and 600 °C for 6 h in an air stream to obtain the non-noble metal oxide powder catalysts CuNiCeO, CuZnMnO, CuZnAlBaO, CuZnZrCeO, CuZnTiO or CuZnMnAlO prepared by the co-precipitation method.

[0122] Q3. Mix the noble metal-loaded powder catalyst prepared in step Q1, the non-noble metal powder catalyst in step Q2, and the Z2 powder carriers Si or SiC with particle sizes of 100 - 250 nm, and calcinate at 550 °C for 5 h in a nitrogen stream to obtain the finished powder catalyst containing noble and non-noble metal dual or multi-active components (Pt-SnO 2 / γ-Al 2 O 3 )-(CuNiCeO) / Si, (Pt-ReO x / (CMK)-CuZnMnO / Si, (Ru-ReO x / (SBA-15)-CuZnAlBaO / SiC, (Pt-SnO 2 / γ-Al 2 O 3 )-CuZnZrCeO / SiC, (Pt-ReO x / (CMK)-CuZnTiO / Si, (Ru-ReO x / (SBA-15)-CuZnMnAlO / Si, abbreviated as PtSn-CuNiCeO / γ-Al 2 O 3 -Si, PtRe-CuZnMnO / CMK-Si, RuRe-CuZnAlBaO / SBA-15-SiC, PtSn-CuZnZrCeO / γ-Al 2 O 3 -SiC, PtRe-CuZnTiO / CMK-Si, RuRe-CuZnMn-AlO / SBA-15-Si, where the first three are respectively labeled as Cat-26 to Cat-28;

[0123] Q4. Add 8 wt% methyl cellulose and 5 wt% water as binders to the finished powder catalyst PtSn-CuZnZrCeO / γ-Al 2 O 3 -SiC, PtRe-CuZnTiO / CMK-Si, RuRe-CuZnMnAlO / SBA-15-Si, extrude into clover-shaped particles with a diameter of 2.2 mm and a length of 3.0 - 5.0 mm, and then calcine in a nitrogen atmosphere at 350 °C for 3 h and 600 °C for 5 h to obtain finished clover-shaped particle catalysts containing noble and non-noble metal dual or multi-active components, and correspondingly labeled as Cat-29 to Cat-31;

[0124] Alternatively, prepare the catalyst according to the catalyst composition formula in Table 5, and the preparation process is as follows:

[0125] Q1. Ball mill and screen the high specific surface porous or mesoporous material Z1 carrier powder, or the high thermal conductivity material Z2 carrier powder, or the mixed powder of Z1 carrier and Z2 carrier to obtain a powder carrier with a particle size of 100 - 250 nm;

[0126] Q2. Prepare aqueous solutions of Component B compound and Component D, an aqueous solution or an alcohol solution of Component C compound, and an aqueous solution of sodium carbonate respectively. While stirring, add these three solutions into the synthesis kettle simultaneously, or add them into the synthesis kettle pre-placed with the powder carrier prepared in Step Q1. Then, cook and age at 80 °C for 2.0 h. Next, filter, wash, dry, and crush the material to obtain the catalyst precursor powder prepared by the co-precipitation method or the deposition-precipitation method.

[0127] Q3. Calcinate the catalyst precursor powder obtained in Step Q2 in an air stream at 350 °C for 3 h and at 600 °C for 6 h to obtain the finished powder catalyst;

[0128] Q4. Add 8 wt% methyl cellulose and 5 wt% water as binders to the finished powder catalyst obtained in Step Q3. Compress and form it into cylindrical particles with a diameter of 2.0 mm and a height of 2.0 mm. Then, calcinate in an air stream at 350 °C for 3 h and at 600 °C for 5 h to obtain the finished particle catalysts CuNiCeO / MS, CuZnCeO / SiO 2 , CuZnAlBaO / SiC, CuZnZrCeO, CuZnTiO / Si, or CuZnMnAlO;

[0129] Q5. Immerse the non-noble metal cylindrical finished particle catalysts CuNiCeO / MS, CuZnCeO / SiO prepared in Step Q4 with an aqueous solution of ruthenium trichloride or chloroplatinic acid, which is Component A compound, for 45 min. After taking them out and drying, calcinate in a nitrogen stream at 350 °C for 2 h and at 600 °C for 5 h to obtain the finished cylindrical particle catalysts containing noble metal and non-noble metal dual or multiple active components Ru-CuNiCeO / MS, Pt-CuZnCeO / SiO 2 , Pt-CuZnAlBaO / SiC, Pt-CuZnZrCeO, Ru-CuZnTiO / Si, or Ru-CuZnMnAlO, and mark them as Cat-32 to Cat-37 respectively. 2

[0130] Table 5 Compositions, morphologies, and corresponding numbers of the catalysts prepared in Examples 26 - 37

[0131] Catalyst Number Catalyst Composition and Mass Percentage of Each Component (%) Z1 Z2 Morphology Cat-26 <![CDATA[0.5Pt5.0Sn-42.0Cu12.5Ni10.0CeO / 22.0γ-Al 2 O 3 -8.0Si]]> <![CDATA[γ-Al 2 O 3 > Si Powder Cat-27 0.5Pt3.0Re-45.0Cu14.0Zn5.5MnO / 22.0CMK-10.0Si CMK Si Powder Cat-28 3.0Ru3.5Re-35.0Cu12.0Zn16.0Al2.5BaO / 20.0(SBA-15)-8.0SiC SBA-15 SiC Powder Cat-29 <![CDATA[0.5Pt5.0Sn-39.0Cu11.0Zn15.0Zr9.5CeO / 10.0γ-Al 2 O 3 -10.0SiC]]> <![CDATA[γ-Al 2 O 3 > SiC Clover Cat-30 1.0Pt3.0Re-36.0Cu10.0Zn15.0TiO / 25.0CMK-10.0Si CMK Si Clover Cat-31 3.5Ru3.5Re-38.0Cu10.0Zn6.0Mn15.0AlO / 15.0(SBA-15)-9.0Si SBA-15 Si Clover Cat-32 5.0Ru-35.0Cu15.0Ni15.0CeO / 30.0MS MS / Cylinder Cat-33 <![CDATA[1.0Pt - 44.0Cu 15.0Zn 10.0CeO / 30.0SiO 2 > <![CDATA[SiO 2 > / Cylinder Cat-34 0.5Pt-40.0Cu14.5Zn30.0Al5.0BaO / 10.0SiC / SiC Cylinder Cat-35 0.5Pt-48.0Cu12.0Zn31.0Zr8.5CeO / / Cylinder Cat-36 3.0Ru-45.0Cu12.0Zn30.0TiO / 10.0Si / Si Cylinder Cat-37 3.0Ru-47.0Cu18.0Zn7.0Mn25.0AlO / / Cylinder

[0132] II. Reduction and activation of the catalyst: Load the finished powder catalyst into a tubular furnace and introduce hydrogen for reduction and activation; or load the finished particle catalyst into a fixed-bed reactor (inter-stage quenching heat exchange adiabatic fixed-bed reactor or shell-and-tube isothermal fixed-bed reactor) and introduce hydrogen for in-situ reduction and activation. Reduction conditions: temperature 380 °C, hydrogen volumetric space velocity 75 h-1 Reduce the hydrogen pressure to 2.0 MPa and continue the reduction until no more water is generated.

[0133] III. Catalytic hydrogenation reaction: Transfer the reduced and activated powder catalyst to an external circulation heat exchange full-mixed slurry bed reactor, or adjust the operating parameters of the fixed bed reactor filled with the in-situ reduced and activated granular catalyst. According to the raw materials (BDO solution of butylene succinate) and concentrations shown in Table 6, and the reaction operating conditions, feed the raw materials and hydrogen to carry out the corresponding hydrogenation reaction of butylene succinate to prepare 1,4-butanediol. The corresponding reaction operating conditions and results are listed in Table 6.

[0134] Table 6 Hydrogenation catalysts, reactor forms, reaction process conditions and results corresponding to Examples 25 - 36

[0135]

[0136]

[0137] From the catalysts, reaction process conditions and results of Examples 26 - 37 listed in Tables 5 and 6, it can be seen that under the operating conditions of BDO solution concentration of butylene succinate being 10 - 60 wt%, feed space velocity of 0.20 - 0.75 h -1 , molar ratio of hydrogen / (ester group and carboxyl group) being 50 - 100, reaction temperature being 160 - 220 °C, and system pressure being 5.0 - 5.5, the conversion rate of butylene succinate is 98.6 - 99.8%, the selectivity of BDO is 93.5 - 96.1%, the selectivity of WXC is 0.9 - 3.1%, the selectivity of GBL is 0.8 - 1.8%, and the selectivity of THF is 0.8 - 3.5%. It shows that the noble metal and non-noble metal dual or multi-active component catalyst has excellent hydrogenation performance for butylene succinate, integrating the respective advantages of noble metal catalysts and non-noble metal catalysts.

[0138] Comparative Examples 2 and 3

[0139] Hydrogenation performance of single noble metal or non-noble metal catalysts without heat conduction carriers

[0140] The catalyst of Example 28 is composed of the noble metal powder catalyst Ru - ReO x / SBA - 15, the non-noble metal powder catalyst CuZnAlBaO, and the heat conduction carrier SiC with a particle size of 100 - 250 nm, and the mass composition is 3.0Ru3.5Re - 35.0Cu12.0Zn16.0Al2.5BaO / 20.0(SBA - 15) - 8.0SiC.

[0141] The catalyst of Comparative Example 2 is the noble metal powder catalyst Ru - ReO of the catalyst of Example 28 x / SBA-15 (mass ratio Ru:Re:SBA-15 = 3.0:3.5:20.0) part, the catalyst of Comparative Example 3 is the non-precious metal powder catalyst CuZnAlBaO of the catalyst of Example 28 (mass ratio CuO:ZnO:Al 2 O 3 :BaO = 35.0:12.0:16.0:2.5) part.

[0142] The activation processes, MBS hydrogenation reaction methods and process conditions of the catalysts of Comparative Examples 2 and 3 are the same as those of Example 28.

[0143] The reaction results of Comparative Example 2 are: MBS conversion rate 83.6%, BDO selectivity 90.5%, WXC selectivity 5.4%, GBL selectivity 2.9% and THF selectivity 1.1%; the reaction results of Comparative Example 3 are: MBS conversion rate 92.5%, BDO selectivity 94.2%, WXC selectivity 2.3%, GBL selectivity 2.1% and THF selectivity 1.2%; the reaction results of Example 28 are: MBS conversion rate 99.8%, selectivity BDO 96.1%, WXC 1.5%, GBL 1.2% and THF 0.8%. It can be seen that under the same conditions, the separate precious metal catalyst (Comparative Example 2) or non-precious metal catalyst (Comparative Example 3) without heat-conducting carrier, compared with the composite catalyst (Example 28) containing heat-conducting carrier SiC, the MBS conversion rate and the product BDO selectivity are both greatly reduced, and the semi-hydrogenation products WXC and GBL increase significantly.

[0144] Comparative Example 4

[0145] Hydrogenation performance of precious metal-non-precious metal catalyst without heat-conducting carrier

[0146] The preparation process of the catalyst of this Comparative Example 4 is different from that of Example 34 in that heat-conducting carrier SiC is not added during the preparation process. The prepared catalyst is Pt-CuZnAlBaO, and its mass composition is Pt:CuO:ZnO:Al 2 O 3 :BaO = 0.5:40.0:14.5:30.0:5.0, while the mass composition of the catalyst Pt-CuZnAlBaO / SiC of Example 34 is Pt:CuO:ZnO:Al 2 O 3 :BaO:SiC = 0.5:40.0:14.5:30.0:5.0:10.0.

[0147] The catalyst activation process and the DBS hydrogenation reaction operation in this comparative example were the same as those in Example 34. The results of the DBS hydrogenation reaction were as follows: the conversion rate of DBS was 99.8%, the selectivity of BDO was 92.8%, the selectivity of WXC was 2.1%, the selectivity of GBL was 1.1%, and the selectivity of THF was 3.8%. Compared with the results of Example 34, it can be seen that the selectivity of the target product BDO decreased significantly, and the selectivity of THF increased significantly. It can be seen that the presence of a heat-conducting carrier in the catalyst structure is beneficial to the hydrogenation of butylene succinate to produce BDO.

[0148] Examples 38 to 51

[0149] Application of noble metal and non-noble metal dual or multi-active component catalysts in the hydrogenation reaction of mono- or diesters of succinic acid

[0150] As shown in Table 7, the catalysts used in Examples 38 to 51 included catalysts Cat26 to 37.

[0151] Reduction activation of the catalyst: The operation process and reduction conditions were the same as those in Example 26.

[0152] Catalytic hydrogenation reaction: Transfer the reduced and activated powder catalyst to an external circulation heat exchange full-mixed slurry bed reactor, or adjust the operation parameters of the fixed bed reactor filled with the in-situ reduced and activated granular catalyst, and feed the raw materials and hydrogen according to the raw materials, concentrations, and reaction operation conditions shown in Table 7 to carry out the corresponding reaction for the hydrogenation of butylene succinate to prepare 1,4-butanediol.

[0153] Among them, the raw materials in Examples 38 to 51 were successively: methanol solution of monomethyl succinate, pure dimethyl succinate, pure monoethyl succinate, pure diethyl succinate, butanol solution of monobutyl succinate, pure dibutyl succinate, isooctanol solution of monoisooctyl succinate, isooctanol solution of diisooctyl succinate, pure diallyl succinate, cyclohexanol solution of dicyclohexyl succinate, BDO solution of monobenzyl succinate, tetrahydrofurfuryl alcohol solution of monotetrahydrofurfuryl succinate, BDO solution of dibutylene glycol diester of succinic acid, and BDO solution of monobutynediol monoester of succinic acid. After hydrogenation, in addition to the main product BDO and a small amount of by-products BGL and THF, the corresponding saturated alcohols (C=C or C≡C are hydrogenated and saturated) corresponding to the succinic acid esters are also co-produced, such as methanol, ethanol, butanol, isooctanol, propanol (from the hydrogenation of allyl alcohol), cyclohexanol, benzyl alcohol, or tetrahydrofurfuryl alcohol. Among them, dibutylene glycol diester of succinic acid and monobutynediol monoester of succinic acid are hydrogenated to produce 3 molecules of BDO and 2 molecules of BDO respectively, and a small amount of unhydrogenated butylene glycol remains. The corresponding reaction operation conditions and results (excluding the co-produced alcohols) are listed in Table 7.

[0154] Table 7 Hydrogenation catalysts, reactor forms, reaction process conditions and results corresponding to Examples 38 to 51

[0155]

[0156]

[0157] From the reaction process conditions and results of Examples 38 to 51 listed in Table 7, it can be seen that at the operating conditions of the liquid concentration of succinic acid ester being 10 - 100 wt%, the feed space velocity being 0.20 - 0.50 h -1 ⁻¹, the molar ratio of hydrogen / (ester group + carboxyl group + double bond) being 50 - 120, the reaction temperature being 170 - 220 °C, and the system pressure being 5.0 - 6.0, the conversion rate of butylene succinate is 98.6 - 100%, the selectivity of BDO is 91.5 - 96.8%, the selectivity of WXC is 0 - 0.9%, the selectivity of GBL is 0.5 - 2.2%, and the selectivity of THF is 1.1 - 6.6%. This indicates that the dual or multi-active component catalyst composed of noble metal and non-noble metal has excellent catalytic hydrogenation performance for both mono-esters or di-esters of succinic acid, and for alkyl, alkenyl, cycloalkyl, aryl, heterocyclic or hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl esters of succinic acid. Moreover, while hydrogenating the ester group and carboxyl group into hydroxyl groups, it also hydrogenates and saturates C═C and C≡C.

[0158] Hydrogenation performance of copper chromite catalyst in Comparative Example 5

[0159] Using the second-stage catalyst copper chromite (52.0Cu42.5Cr5.5BaO) of Patent CN103946201B and the same reaction mode and process conditions as in Example 39, that is: the concentration of dimethyl succinate (DMS) in the raw material is 100%, the feed space velocity is 0.2 h -1 ⁻¹, the temperature is 185 °C, the hydrogen / ester molar ratio is 75, and the pressure is 5.0 MPa. The conversion rate of DMS is 97.8%, the selectivity of BDO is 80.5%, the selectivity of GBL is 5.2%, and the selectivity of THF is 9.6%. DMS is hydrogenated to produce BDO and by-products GBL and THF,

[0160] Comparing Example 39 and Comparative Example 5, it can be seen that under the same reaction mode and process conditions, the catalyst 1.0Pt3.0Re-36.0Cu10.0Zn15.0TiO / 25.0CMK-10.0Si prepared by the impregnation-coprecipitation-mixing method in the present invention (the conversion rate of DMS is 99.5%, the selectivity of BDO is 95.6%, the selectivity of GBL is 1.0%, and the selectivity of THF is 3.1%) has significantly higher hydrogenation activity and selectivity than the catalysts of the prior art.

[0161] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A catalyst for preparing 1,4-butanediol by hydrogenation of succinate, characterized in that: The structural formula is: aAbBcCdD / (xZ1+yZ2); Wherein: component A is selected from at least one of the noble metals Ru, Os, Rh, Ir, Pd or Pt, component B is selected from at least one of the transition metals Cr, Mn, Fe, Co, Ni or Cu, component C is selected from at least one of the oxides of Ga, In, Ge, Sn, Pb, Sb, Bi, Se, Te, Nb, Mo, W, Re, Al, Ti, Zr or Zn, component D is an oxide of at least one of the alkaline earth or rare earth metals, Z1 is a high specific surface area carrier selected from carbon materials, light magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, zeolite molecular sieve, hydroxyapatite, diatomaceous earth, bentonite, kaolin Or at least one of attapulgite, Z2 is a high thermal conductivity carrier selected from at least one of graphite, graphene, α-Al2O3, Si, α-SiO2, BeO, SiC, Mo2C, BN or AlN; the mass percentage of each component is: a=0.1~10wt%, b=0~60wt%, c=0~50wt%, d=0~20wt%, x=10~90wt%, y=0~40wt%; or, a=0, b=15~70wt%, c=0~80wt%, d=0~15wt%, x=0~45wt%, y=0~20wt%, and c and d are not 0 at the same time.

2. The catalyst for preparing 1,4-butanediol by hydrogenation of succinate according to claim 1, characterized in that: The catalyst is a single noble metal or dual noble metal active component catalyst, or a dual active component catalyst composed of a single noble metal and a single non-noble metal; wherein A is selected from one or two of Ru, Os, Rh, Ir, Pd or Pt, B is selected from one of Cr, Mn, Fe, Co, Ni or Cu, C is selected from at least one metal oxide of Ga, In, Ge, Sn, Pb, Sb, Bi, Se, Te, Nb, Mo, W, Re or Zn, and D is selected from Mg, Ca, Sr, B an oxide of at least one of the following metals: a, Sc, Y, La, Ce, Nd, Sm, Er, Yb or Th; Z1 is selected from activated carbon, mesoporous carbon, carbon nanotubes, light MgO, amorphous Al2O3, γ-Al2O3, θ-Al2O3, mesoporous Al2O3, amorphous SiO2, silica gel, mesoporous SiO2, amorphous TiO2, rutile, anatase, mesoporous TiO2, ZrO2, mordenite, clinoptilolite, Y zeolite, β zeolite, ZSM-5, ZSM-1 1. ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-41, MCM-48, MCM-49, MCM-50, MCM-56 , SCM-14, SCM-15, AlPO4-11, SAPO-11, SAPO-34, ZRP-3, Silicalite-1, Silicalite-2, TS-1, TS-2, SBA -15, ZEO-2, ZEO-3, KIT-6, HAP, at least one of diatomaceous earth, bentonite, kaolin or attapulgite, Z2 is selected from at least one of graphite, graphene, α-Al2O3, Si, α-SiO2, BeO, SiC or Mo2C; and the mass percentage of each component is: a=0.5~10wt%, b=0~15wt%, c=0~10wt%, d=0~10wt%, x=60~90wt%, y=0~35wt%.

3. The catalyst for preparing 1,4-butanediol by hydrogenation of succinate according to claim 2, characterized in that: A is selected from one or two of Ru, Pd or Pt, B is selected from one of Mn, Fe, Ni or Cu, C is selected from one or two oxides of Ga, In, Sn, Nb, Mo, W, Re or Zn, D is selected from one or two oxides of Mg, Ba, La or Ce, and Z1 is selected from one of AC, CMK, γ-Al2O3, θ-Al2O3, silica gel, MS, SiO2-Al2O3, anatase, ZrO2, MCM-41, MCM-48, S-1, TS-1, SBA-15, HAP, diatomaceous earth or bentonite Preferably, the mass percentage of each component is: a=1.0-5.00%, b=0-10.00%, c=0-10.00%, d=0-5.00%, x=60.00-86.00%, y=0-30%; preferably, the mass percentage of each component is: a=1.0-5.00%, b=0-10.00%, c=0-10.00%, d=0-5.00%, x=60.00-86.00%, y=10-30%.

4. The catalyst for preparing 1,4-butanediol by hydrogenation of succinate according to claim 1, characterized in that: The catalyst is a single non-precious metal or dual non-precious metal active component catalyst, wherein B is selected from one or two of Cr, Mn, Fe, Co, Ni or Cu, C is selected from the oxide of at least one metal of Ga, In, Mo, W, Re, Al, Ti, Zr or Zn, D is selected from the oxide of at least one metal of Mg, Ba, Sc, Y, La, Ce, Nd or Yb, and Z1 is selected from amorphous Al2O3, γ-Al2O3, θ-Al2O3, MA, amorphous SiO2, silica gel, MS, TiO2, ZrO2, MC At least one of M-41, MCM-48, MCM-50, S-1, S-2, TS-1, TS-2, SBA-15, ZEO-2, ZEO-3, KIT-6, diatomaceous earth, bentonite, kaolin or attapulgite, Z2 is selected from at least one of α-Al2O3, Si, α-SiO2, BeO, SiC or Mo2C; the mass percentage of each component is: a=0, b=18~70%, c=0~80%, d=0~15%, x=0~45%, y=0~20%, c and d are not 0 at the same time.

5. The catalyst for preparing 1,4-butanediol by hydrogenation of succinate according to claim 4, characterized in that: In the single non-precious metal or double non-precious metal active component catalyst, B is selected from one or two of Cr, Mn, Fe, Co, Ni or Cu, C is selected from one or two metal oxides of Ga, In, Mo, Al, Ti, Zr or Zn, D is selected from one or two metal oxides of Mg, Ba, La or Ce, Z1 is selected from at least one of γ-Al2O3, θ-Al2O3, MA, silica gel, MS, TiO2, ZrO2, MCM-41, MCM-48, S-1, TS-1, SBA-15, HAP, diatomaceous earth or bentonite, and Z2 is selected from at least one of α-Al2O3, Si, α-SiO2 or SiC; the mass percentage of each component is: a=0, b=40-70%, c=0-50%, d=0-10%, x=0-40%, y=0-15%, and c and d are not 0 at the same time.

6. The catalyst for preparing 1,4-butanediol by hydrogenation of succinate according to claim 5, characterized in that: In the single non-noble metal or dual non-noble metal active component catalyst, B is Cu or B is Cu and one of Cr, Mn, Fe, Co or Ni, and the mass percentage of Cu is 40-55%.

7. The catalyst for preparing 1,4-butanediol by hydrogenation of succinate according to claim 1, characterized in that: The catalyst is a multi-active component catalyst composed of noble metals and non-noble metals, wherein A is selected from at least one of Ru, Os, Rh, Ir, Pd or Pt, B is selected from at least one of Cr, Mn, Fe, Co, Ni or Cu, C is selected from at least one of Mo, W, Re, Al, Ti, Zr or Zn oxides, D is selected from at least one of Mg, Ba, Sc, Y, La, Ce, Nd or Yb oxides, and Z1 is selected from AC, CMK, CNT, light MgO, amorphous Al2O3, γ-Al2O3, θ-Al2O3, MA, amorphous SiO2, silica gel, MS, TiO2, ZrO2, MOR, HEU, Y, β, ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZS At least one of M-48, MCM-22, MCM-41, MCM-48, MCM-49, MCM-50, MCM-56, SCM-14, SCM-15, AlPO4-11, SAPO-11, SAPO-34, ZRP-3, S-1, S-2, TS-1, TS-2, SBA-15, ZEO-2, ZEO-3, KIT-6, HAP, diatomaceous earth, bentonite, kaolin or attapulgite, Z2 is selected from at least one of graphite, graphene, α-Al2O3, Si, α-SiO2, BeO, SiC, Mo2C, BN or AlN, and the mass percentage of each component is: a=0.1~5.0%, b=30~60%, c=0~50%, d=0~20%, x=0~40%, y=0~15%, and c and d are not 0 at the same time.

8. The catalyst for preparing 1,4-butanediol by hydrogenation of succinate according to claim 7, characterized in that: A is selected from at least one of Ru, Pd or Pt, B is selected from at least one of Mn, Fe, Co, Ni or Cu, C is selected from at least one of Mo, Al, Ti, Zr or Zn oxides, D is selected from one or two of Mg, Ba, La or Ce oxides, Z1 is selected from AC, γ-Al2O3, silica gel, TiO2, ZrO2, ZSM-5, MCM-22, MCM-41, MCM-48, SCM-14, SAPO-3 4. One or two of ZRP-3, S-1, TS-1, SBA-15, HAP, diatomaceous earth or bentonite, Z2 is selected from one or two of α-Al2O3, Si, α-SiO2, SiC or BN; the mass percentage of each component is a=0.5-3.00%, b=35.00-55.00%, c=0-45.00%, d=0-15.00%, x=0-30%, y=0-10.00%, and c and d are not 0 at the same time.

9. Use of the catalyst according to any one of claims 1 to 8, characterized in that: The catalyst is used for the reaction of hydrogenating succinate to prepare 1,4-butanediol. The process of the hydrogenation reaction is as follows: a raw material succinate solution preheated to a temperature of 120-180° C. and a concentration of 10-100 wt % is fed into a slurry bed or fixed bed reactor filled with the catalyst that has been pre-reduced and activated to carry out a catalytic hydrogenation reaction to obtain a 1,4-butanediol product; the process conditions of the hydrogenation reaction are: the succinate solution feed weight hourly space velocity is 0.05-2.00 h -1 , reaction temperature 140-300°C, hydrogen pressure 1.5-10.0MPa, hydrogen-ester molar ratio 20-200; Preferably, the process conditions of the hydrogenation reaction are: feed weight hourly space velocity 0.10~1.50h -1 , reaction temperature 150-280°C, hydrogen pressure 2.0-8.0 MPa, hydrogen-ester molar ratio 35-150; more preferably, feed weight hourly space velocity 0.20-1.00 h -1 , reaction temperature 160-260°C, hydrogen pressure 2.5-6.5MPa, hydrogen-ester molar ratio 50-100.

10. The use according to claim 9, characterized in that: The succinates include succinic acid monoesters and / or diesters of monohydric alcohols, or succinic acid monoesters, diesters, polyesters and / or di- or poly-succinic acid diesters or polyesters of dihydric or polyhydric alcohols; wherein: The monohydric alcohol includes C1~C 20 Fatty alcohol, C7~C 16 Aromatic alcohol, C3~C 16 Heterocyclic alcohols or substituted alcohols thereof; preferably methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, isopentanol, neopentyl alcohol, isooctyl alcohol, allyl alcohol, butenol, isopentenol, propargyl alcohol, butynol, cyclopentanol, cyclohexanol, 4-methylcyclohexanol, cyclohexylmethanol, cyclohexylethanol, cyclohexylpropanol, benzyl alcohol, α-phenylethanol, β-phenylethanol, α-methylphenylethanol, hydrocinnamic alcohol, cinnamic alcohol, glycidol, furfuryl alcohol, tetrahydrofurfuryl alcohol, nicotinic alcohol, 2-pyridinemethanol, 4-piperidinemethanol, 2-thiophenemethanol, 2-chloroethanol, 3-chloropropanol, 4-chlorobutanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol; more preferably methanol, ethanol, butanol or isooctyl alcohol; The dihydric or polyhydric alcohol includes C2 to C 10 Fatty diols or polyols, C8~C 16 Aromatic diols, C5~C 10 Heterocyclic diols or substituted alcohols thereof; preferably ethylene glycol, diethylene glycol, triethylene glycol, oligoethylene glycol (PEG), 1,2-propylene glycol, dipropylene glycol, oligopropylene glycol (PPG), 1,3-propylene glycol, 1,4-butanediol, oligotetramethylene ether glycol (PTMEG), 1,4-butene diol, 1,4-butynediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol (glycerol), trimethylolethane, trimethylolpropane, pentaerythritol, erythritol, xylitol, mannitol , sorbitol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, o-phthalic acid methanol, isophthalic acid methanol, p-phthalic acid methanol, 1,4-naphthalene dimethanol, 1,8-naphthalene dimethanol, 2,2′-biphenyl dimethanol, 4,4′-biphenyl dimethanol, 2,5-furan dimethanol, 2,6-pyridine dimethanol; more preferably 1,4-butanediol, 1,4-butenediol or 1,4-butynediol.

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