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Method for preparing hydrocarbon from higher aliphatic ester by metal phosphide catalyst

A technology of metal phosphide and higher fatty acid, applied in the field of hydrocarbon production, can solve the problems that precious metals affect large-scale application, increase investment and operating costs, and affect diesel quality, etc., and achieve the effects of good application prospects, low cost, and high activity.

Inactive Publication Date: 2012-07-18
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the sulfur content in vegetable oils is very low. When using sulfide catalysts, it is necessary to add a sulfide agent to the raw material to maintain the sulfide state of the catalyst to inhibit its deactivation. This will not only increase investment and operating costs, but also generate sulfur-containing by-products. The high cost of precious metals such as Pd will affect its large-scale application

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0009] Embodiment 1. A certain amount of carrier SiO 2 Dry at 110°C for 4 hours, use Ni(NO 3 ) 2 and NH 4 h 2 PO 4 Mixed solution impregnated SiO 2 The carrier was dried for 12 hours at 110° C. for 12 hours, and then calcined at 500° C. for 4 hours in an air atmosphere to prepare a catalyst precursor. Put 1.5 grams of this precursor in a quartz tube reactor, feed in hydrogen gas with a flow rate of 320 ml / min, first raise the temperature from room temperature to 250 °C at a rate of 5 °C / min, and then increase the temperature at a rate of 1 °C / min to 650°C, and after maintaining at 650°C for 3 hours, SiO can be prepared 2 Supported nickel phosphide catalyst, the catalyst at room temperature with 0.5% O 2 / N 2 Air flow (100 ml / min) passivated for 6 hours before use. XRD test results show that the prepared catalyst is SiO 2 load Ni 2 P, the mass contents of nickel and phosphorus in the catalyst were 13.4% and 3.9%, respectively.

[0010] Using methyl dodecanoate as th...

Embodiment 2

[0011] Embodiment 2. Catalyst preparation process is the same as embodiment 1, and difference is that prepared catalyst is SiO 2 load Ni 3 P, the mass content of nickel and phosphorus in the catalyst are 14.1% and 2.1% respectively. The reaction performance evaluation of catalyst and product analysis are the same as embodiment 1, and difference is that temperature of reaction is 340 o c. Calculated by mass, the conversion of methyl dodecanoate was 98.5%, and the total selectivity of products C11 and C12 hydrocarbons was 70.5%.

Embodiment 3

[0012] Embodiment 3. Catalyst preparation process is the same as embodiment 1, difference is prepared SiO 2 load Ni 2 The mass contents of Ni and P in the P catalyst were 3% and 1%, respectively. The reaction performance evaluation of catalyst and product analysis are the same as embodiment 1, and difference is that temperature of reaction is 360 o c. Calculated by mass, the conversion rate of methyl dodecanoate was 97.5%, and the total selectivity of products C11 and C12 hydrocarbons was 73.2%.

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Abstract

The invention discloses a method for preparing hydrocarbon from higher aliphatic ester by taking metal phosphide as a catalyst. The method comprises the following steps: filling the metal phosphide catalyst in a fixed bed reactor; feeding in the molar ratio of hydrogen to higher aliphatic ester of (10-500):1; under the conditions that the temperature is 250-450DEG C and H2 pressure is 0.1-8.0MPa and the weight hourly space velocity of higher aliphatic ester is 0.1-15h<-1>, generating hydrocarbon, wherein the metal phosphide catalyst takes silicon dioxide, aluminum oxide, HY molecular sieve, HZSM-5 molecular sieve, titanium dioxide-aluminum oxide composite oxide or cerium oxide-aluminum oxide composite oxide as a carrier, the active phase of hydrocarbon is phosphide of Ni, Co, Fe, Mo, W, Ni-Co, Ni-Fe, Ni-MO, Ni-W or Co-Mo, and the mass of the metal element and the mass of the phosphorus element respectively account for 30-40wt% and 1-15% of that of the catalyst. According to the invention, the adopted metal phosphide catalyst has the advantages of high activity, low cost, good application prospect and the like and does not need to use a vulcanizing agent.

Description

technical field [0001] The invention relates to a method for deoxygenating hydrocarbons from higher fatty acid esters with metal phosphide catalysts, and belongs to the technical field of hydrocarbon production. Background technique [0002] With the increasing shortage of fossil resources such as oil, natural gas and coal, the development and utilization of renewable resources has attracted worldwide attention. Biomass is the only renewable energy source that can be converted into carbon-containing liquid fuels. Biodiesel produced from animal and vegetable oils has become an important substitute for petroleum. The main components of animal and vegetable oils and fats are saturated or unsaturated triglycerides. Fatty acid methyl esters produced by transesterification are called first-generation biodiesel, and those obtained through hydrodeoxygenation and isomerization are similar to petroleum-based diesel components. Alkanes are called second-generation biodiesel. Compare...

Claims

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Application Information

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IPC IPC(8): C10G3/00
CPCY02P30/20
Inventor 陈吉祥李克伦李莉石恒
Owner TIANJIN UNIV
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